Substituted pyridazinones as herbicides

Abstract

To provide: herbicidal substituted phenyl-pyridazine-diones and substituted phenyl-pyridazinone derivatives of formula (I); and processes and intermediates used for the preparation of such derivatives.SOLUTION: The present invention relates to: herbicidal substituted phenyl-pyridazine-diones and substituted phenyl-pyridazinone derivatives of formula (I); and processes and intermediates used for the preparation of such derivatives. The invention further provides: herbicidal compositions comprising such derivatives; and the use of such compounds and compositions in controlling undesirable plant growth, in particular the use in controlling weeds, such as broad-leaved dicotyledonous weeds, in crops of useful plants.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to herbicidal substituted phenyl-pyridazine-dione and substituted phenyl-pyridazinone derivatives of formula (I) and to processes and intermediates used in the preparation of such derivatives. The invention further extends to herbicidal compositions containing such derivatives and to the use of such compounds and compositions in the control of undesirable plant growth: in particular in the control of weeds, such as broadleaf dicotyledonous weeds, in crops of useful plants. [Background technology]

[0002] Herbicidal pyridazinones are known from WO 2009 / 086041.Furthermore, herbicidal 5 / 6-membered heterocyclyl-substituted pyridazinones are known from WO 2011 / 045271.On the other hand, WO 2013 / 160126 describes indolyl-pyridazinone derivatives that exhibit herbicidal activity. Summary of the Invention [Means for solving the problem]

[0003] The present invention is based on the discovery of substituted phenyl-pyridazine-dione and substituted phenyl-pyridazinone derivatives of formula (I), which exhibit unexpectedly good herbicidal activity.

[0004] Thus, in a first embodiment, a compound of formula (I) [ka] or a salt or N-oxide thereof, wherein R 1 is selected from the group consisting of C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 alkoxy, C1-C2 alkoxy-C1-C2 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, cyano-C1-C4 alkyl, C2-C4 haloalkenyl, C2-C4 alkynyl, and C2-C4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C6 alkoxy, C1-C3 alkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, -S(O) m Selected from the group consisting of C1-C6 alkyl, amino, C1-C6 alkylamino, C1-C6 dialkylamino, -C(C1-C3 alkyl)=NO-C1-C3 alkyl, and C2-C6 haloalkynyl; G is hydrogen or C(O)R 3 and; R 3 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl-S-, C1-C6 alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, and C3-C6 cycloalkyl, or R 4 and R 5 can be taken together to form a morpholinyl ring; Each R 4a and R 5a are independently selected from the group consisting of C1-C6 alkoxy and C3-C6 cycloalkyl, or R 4a and R 5a can be taken together to form a morpholinyl ring; R 6 is selected from the group consisting of halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy; X and Y are each independently hydrogen, C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen; D is R on at least one ring carbon atom. 8 and / or substituted on at least one ring nitrogen atom with R 9 is a substituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with At least one R 8 is C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, -NR 4a R 5a , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5, C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; and ring systems selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, said ring systems being selected from the group consisting of 0-5 R 16 is replaced by; At least one R 9 is C5-C6 alkyl, C5-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C3 alkyl-, C3 alkoxy-C1-C2 alkyl-, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, and ring systems selected from the group consisting of phenyl rings, 5-6 membered heteroaryl rings and 3-6 membered heterocyclyl rings, said ring systems being selected from the group consisting of 0-5 R 16 is replaced by; m is an integer of 0, 1, or 2; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy; Or D is at least one R 8 is a phenyl ring substituted with; W is [ka] where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the attachment point to ring D, R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C1-C3 alkyl, or C1-C3 haloalkyl; Or R 10 and R 12 form, together with the carbon atoms to which they are attached, a C3-C6 carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl; However, R 11 or R 13 When one of is halogen, C1-C3 alkyl, or C1-C3 haloalkyl, the other is hydrogen.

[0005] In a second aspect, a compound of formula (I) [ka] or a salt or N-oxide thereof, wherein R 1 is selected from the group consisting of C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 alkoxy, C1-C2 alkoxy-C1-C2 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, cyano-C1-C4 alkyl, C2-C4 haloalkenyl, C2-C4 alkynyl, and C2-C4 haloalkynyl; R 2is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C6 alkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, -S(O) m C1-C6 alkyl, -NR 4 R 5 , -C(C1-C3 alkyl)=NO-C1-C3 alkyl, and C2-C6 haloalkynyl; G is hydrogen or C(O)R 3 and; R 3 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl-S-, C1-C6 alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, and C3-C6 cycloalkyl, or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is selected from the group consisting of halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy; X is cyclopropyl (preferably X is ortho relative to the pyridazinone / pyridazinedione moiety); Y is hydrogen, C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen (Y is ortho (3 position) relative to the -WD moiety); D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is preferably R 8 and / or substituted on the ring nitrogen atom with R 9 is replaced by; Each R 8 are independently oxygen, hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4 R 5 , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5, C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0 to 5 R 16 is replaced by; m is an integer of 0, 1, or 2 (preferably, 0 or 2); Each R 9 are independently C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is replaced by; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is replaced by; W is [ka] where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the attachment point to ring D, R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C1-C3 alkyl, or C1-C3 haloalkyl; Or R 10 and R 12 form, together with the carbon atoms to which they are attached, a C3-C6 carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl; However, R 11 or R 13 When one of is halogen, C1-C3 alkyl, or C1-C3 haloalkyl, the other is hydrogen.

[0006] In a third aspect, a compound of formula (I) [ka] or a salt or N-oxide thereof, wherein R 1 is selected from the group consisting of C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 alkoxy, C1-C2 alkoxy-C1-C2 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, cyano-C1-C4 alkyl, C2-C4 haloalkenyl, C2-C4 alkynyl, and C2-C4 haloalkynyl; R 2is hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C6 alkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, -S(O) m C1-C6 alkyl, -NR 4 R 5 , -C(C1-C3 alkyl)=NO-C1-C3 alkyl, and C2-C6 haloalkynyl; G is hydrogen or C(O)R 3 and; R 3 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl-S-, C1-C6 alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, and C3-C6 cycloalkyl, or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is selected from the group consisting of halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy; X is hydrogen, C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen (preferably X is ortho relative to the pyridazinone / pyridazinedione moiety); Y is cyclopropyl (preferably Y is ortho relative to the -WD moiety); D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is preferably R 8 and / or substituted on the ring nitrogen atom with R 9 is replaced by; Each R 8 are independently oxygen, hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4 R 5 , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5, C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0 to 5 R 16 is replaced by; m is an integer of 0, 1, or 2; Each R 9 are independently C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is replaced by; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is replaced by; W is [ka] where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the attachment point to ring D, R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C1-C3 alkyl, or C1-C3 haloalkyl; Or R 10 and R 12 form, together with the carbon atoms to which they are attached, a C3-C6 carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl; However, R 11 or R 13 When one of is halogen, C1-C3 alkyl, or C1-C3 haloalkyl, the other is hydrogen.

[0007] The compounds of formula (I) may contain asymmetric centers and may exist as single enantiomers, pairs of enantiomers in any ratio, or, if two or more asymmetric centers are present, all possible ratios of diastereoisomers. Typically, one of the enantiomers has improved biological activity compared to the other possible enantiomers.

[0008] Similarly, when disubstituted alkenes are present, these may be present in the E or Z form or as a mixture of both in any proportion.

[0009] Furthermore, compounds of formula (I) may be in equilibrium with other tautomers. For example, compounds of formula (Ii), i.e., compounds of formula (I) (wherein R 2 where is hydrogen and G is hydrogen, can be depicted as at least three tautomers: [ka]

[0010] It should be understood that all tautomers (single tautomers or mixtures thereof), racemic mixtures and single isomers are included within the scope of the present invention.

[0011] Each alkyl moiety, alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, or dialkylaminocarbonyl), may be linear or branched. Typically, the alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl group is generally a C1-C6 alkyl group (unless already defined more narrowly), but is preferably a C1-C4 alkyl or C1-C3 alkyl group, and more preferably a C1-C2 alkyl group (such as methyl).

[0012] The alkenyl and alkynyl moieties may be in the form of straight or branched chains, and the alkenyl moieties may be of either the (E)- or (Z)-configuration, as appropriate. The alkenyl or alkynyl moiety is typically a C2-C4 alkenyl or a C2-C4 alkynyl, more particularly vinyl, allyl, ethynyl, propargyl or prop-1-ynyl. The alkenyl and alkynyl moieties may contain one or more double and / or triple bonds in any combination; however, preferably, they contain only one double bond (in the case of alkenyl) or only one triple bond (in the case of alkynyl).

[0013] Preferably, the term cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0014] In the present context, the term "aryl" preferably means phenyl. The term "heteroaryl" as used herein means an aromatic ring system containing at least one ring heteroatom and consisting of a single ring. Preferably, the single ring contains 1, 2 or 3 ring heteroatoms independently selected from nitrogen, oxygen and sulfur. Typically, "heteroaryl" is furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl.

[0015] Heterocyclyl groups and heterocyclic rings (alone or as part of a larger group, e.g., heterocyclyl-alkyl-) are ring systems containing at least one heteroatom and may be in monocyclic or bicyclic form. Preferably, heterocyclyl groups contain up to two heteroatoms, preferably selected from nitrogen, oxygen and sulfur. Examples of heterocyclic groups include oxetanyl, thietanyl, azetidinyl and 7-oxa-bicyclo[2.2.1]hept-2-yl. Heterocyclyl groups containing a single oxygen atom as the heteroatom are most preferred. Heterocyclyl groups are preferably 3-8 membered, more preferably 3-6 membered, monocyclic rings, which may be fully or partially saturated.

[0016] Halogen (or halo) includes fluorine, chlorine, bromine or iodine. Correspondingly, the same applies to halogen in the context of other definitions such as haloalkyl or halophenyl.

[0017] Haloalkyl groups having a chain length of 1 to 6 carbon atoms are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.

[0018] The alkoxy group preferably has a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or pentyloxy or hexyloxy isomers, preferably methoxy and ethoxy. It should also be understood that two alkoxy substituents may be present on the same carbon atom.

[0019] Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.

[0020] C1 to C6 alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

[0021] C1-C6 alkyl-S(O)-(alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

[0022] C1-C6 alkyl-S(O)2-(alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

[0023] base Q [ka] is referred to herein as the pyridazinedione / pyridazinone moiety, where B indicates the point of attachment to the remainder of the molecule (ie, the optionally substituted phenyl WD moiety).

[0024] The present invention also includes agriculturally acceptable salts that the compounds of formula (I) may form with amines (e.g. ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the hydroxides, oxides, alkoxides and hydrogencarbonates and carbonates of alkali metals and alkaline earth metals used as salt formers, emphasis is placed on the hydroxides, alkoxides, oxides and carbonates of lithium, sodium, potassium, magnesium and calcium, but especially on the hydroxides, alkoxides, oxides and carbonates of sodium, magnesium and calcium. The corresponding trimethylsulfonium salts may also be used. The compounds of formula (I) according to the present invention also include hydrates that may form during salt formation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] R1 , R 2 , R 3 , R 4 , R 5 , R 4a , R 5a , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 Preferred values ​​for , W, D, Dp, G, X, Y, and m are as described below, and the compounds of formula (I) according to the present invention may include any combination of said values. Those skilled in the art will understand that any given set of values ​​of an embodiment may be combined with any other set of values ​​of an embodiment, if the combinations are not mutually exclusive.

[0026] Preferably, R 1 is selected from the group consisting of methyl, ethyl, propyl (especially n- or c-propyl), propargyl or C1 haloalkyl. More preferably, R 1 is methyl, ethyl, cyclopropyl, propargyl or C1 fluoroalkyl. Even more preferably, R 1 is methyl, ethyl, cyclopropyl or propargyl. Most preferably, R 1 is methyl.

[0027] Preferably, R 2 is selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C3 alkoxy-C1-C3 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl and C2-C6 haloalkynyl. More preferably, R 2is selected from the group consisting of chloro, fluoro, methyl, ethyl, cyclopropyl, trifluoromethyl and methoxymethyl, even more preferably chloro, cyclopropyl, trifluoromethyl or methyl, most preferably chloro or methyl. In one set of embodiments of the present invention, R 2 is hydrogen. In a further set of embodiments, R 2 is cyclopropyl, and in a third set of embodiments, R 2 is methyl, and in a fourth set of embodiments, R 2 is trifluoromethyl, and in a fifth set of embodiments, R 2 is chloro.

[0028] As described herein, G is hydrogen or -C(O)-R 3 R 3 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkyl-S-, C1-C6 alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with

[0029] As defined herein, R 4 and R 5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy-, and C3-C6 cycloalkyl; or they can be taken together to form a morpholinyl ring. The substituents G (and also R 3 ) in the situation of R 4 and R 5 are preferably each independently selected from the group consisting of methyl, ethyl, propyl, methoxy, ethoxy and propoxy, each R 34 and R 35 Other substituents (e.g., R 2 , R 8 ) in the situation of R 4 and R 5are preferably each independently hydrogen, C1-C3 alkyl, C1-C3 alkoxy, or C3-C6 cycloalkyl, and each R 84 and R 85 Multiple R 4 The larger moiety, e.g., the group -NR 4 C(O)NR 4 R 5 If included in each R 4 are independent, so in such a part, two R 4 One skilled in the art will recognize that the groups can be the same or they can be different from one another.

[0030] R 6 is selected from the group consisting of halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy and C1-C3 haloalkoxy. 6 is selected from the group consisting of halogen, C1-C3 alkyl, and C1-C3 haloalkyl.

[0031] Preferably, R 3 is C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, -C1-C4 alkoxy, -NR 4 R 5 and R 4 and R 5 together form a morpholinyl ring, or phenyl. More preferably, R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy. More preferably, R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy.

[0032] In one set of embodiments, G is hydrogen or -C(O)-R 3 where R 3 is C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, or -C1-C4 alkoxy. In a further set of embodiments, G is hydrogen or -C(O)-R 3where R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl or methoxy. However, G is hydrogen or -C(O)-R 3 where R 3 However, isopropyl is particularly preferred.

[0033] When Y is cyclopropyl, X is preferably hydrogen, cyclopropyl, halogen, or C1 haloalkyl, more preferably hydrogen, fluoro, chloro, bromo, or C1 fluoroalkyl, more preferably also hydrogen, fluoro, chloro, or trifluoromethyl. Most preferably, when Y is cyclopropyl, X is fluoro. In one set of embodiments, X is preferably ortho (6-position) relative to the pyridazinone / pyridazinedione moiety (group Q). It is particularly preferred that X is fluoro, chloro, or C1-haloalkyl (particularly C1 fluoroalkyl) and ortho (6-position) relative to the pyridazinone / pyridazinedione moiety (group Q). Most preferably, X is fluoro and ortho (6-position) relative to the pyridazinone / pyridazinedione moiety (group Q).

[0034] When X is cyclopropyl, in such embodiments, Y is preferably hydrogen, C1-C3 alkyl, cyclopropyl, C1-C3 haloalkyl, or halogen, more preferably Y is hydrogen, chloro, fluoro, or bromo. Most preferably, when X is cyclopropyl, Y is chloro.

[0035] In one set of embodiments, it is preferred that Y is ortho (position 3) to the WD moiety. In a further set of embodiments, Y is para to the pyridazinone / pyridazine-dione moiety (group Q).

[0036] It is especially preferred that Y is ortho (position 3) to the WD moiety and is halogen, especially chloro or fluoro; more preferably chloro.

[0037] As described herein, D is a substituted or unsubstituted phenyl ring (Dp) or a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is a substituted heteroaryl ring or a substituted phenyl ring, it is selected from the group consisting of R 8 and / or, in the case of heteroaryl rings, substituted on the ring nitrogen atom by R 9 When D is a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring, it is preferably a substituted (as described herein) or unsubstituted furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl ring.

[0038] In such embodiments, D is preferably a substituted (as described herein) or unsubstituted pyridyl, pyrazolyl, thiazolyl, pyrimidinyl, thienyl, triazolyl or oxadiazolyl ring, more preferably a pyridyl ring.

[0039] In one set of embodiments, D is a substituted (as described herein) or unsubstituted pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridonyl, pyrimidinyl, pyridazinyl, or pyrazinyl ring.

[0040] In a further set of such embodiments, D is a substituted (as described herein) or unsubstituted oxazolyl, thiazolyl, or pyridyl ring. In certain embodiments, D is a substituted or unsubstituted pyridyl ring, or a substituted or unsubstituted thiazolyl ring.

[0041] R 8 The substitution of D by is determined by the presence or absence of cyclopropyl at positions X and / or Y. However, in general, when D is a substituted 5- or 6-membered heteroaryl ring, it is preferably substituted by one or two R 8 and / or 1 R 9 More preferably, one or two R 8 When D is a 5-membered substituted heteroaryl ring, it is most preferably substituted with one R 8 When D is a substituted phenyl ring, it is preferably substituted with one or two R 8 , more preferably one R 8 has been replaced with.

[0042] When at least one of X and Y is cyclopropyl and D is substituted, each R 8 is hydrogen, oxygen, hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O)m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4 R 5 , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, -NR 4 C(O)NR 4 R 5 , C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring and a 3- to 6-membered heterocyclyl ring, wherein the ring system is independently selected from the group consisting of 0 to 5 R 16 is replaced by; m is an integer of 0, 1, or 2 (preferably, 0 or 2); 9are independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is replaced by; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy.

[0043] When both X and Y are other than cyclopropyl and D is a phenyl ring, D is preferably C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, -NR 4a R 5a , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3- C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or at least one R selected from the group consisting of a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring. 8 and the ring system is substituted with 0 to 5 R 16 m, R 4 , R 5 and R 16 is as defined herein.

[0044] As defined herein, in the situation where both X and Y are other than cyclopropyl, each R 4a and R 5a are independently selected from the group consisting of C1-C6 alkoxy and C3-C6 cycloalkyl, or R 4 and R 5 together can form a morpholinyl ring.

[0045] Any further R 8The substituents are oxygen, hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4 R 5 , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, -NR 4 C(O)NR 4 R 5, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, wherein the ring system is selected from the group consisting of 0-5 R 16 m, R 4 , R 5 and R 16 is as defined herein.

[0046] When both X and Y are other than cyclopropyl and D is a monocyclic heteroaryl ring, D may be selected from the group consisting of C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4a R 5a , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3- at least one R selected from the group consisting of C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring; 8 and the ring system is substituted with 0 to 5 R 16 and / or D is substituted on the ring nitrogen with C5-C6 alkyl, C5-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C3 alkyl-, C3 alkoxy-C1-C2 alkyl-, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m At least one R selected from the group consisting of -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring. 9 and the ring system is substituted with 0 to 5 R 16 m, R 4 , R 5 , R 4a , R 5aand R 16 is as defined herein.

[0047] In such embodiments, when both X and Y are other than cyclopropyl, any additional ring carbon R 8 The substituents are oxygen, hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl-, C1-C6 alkylcarbonyl-, C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, -NR 4 R 5 , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5, C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3-C 6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 m, R 4 , R 5 and R 16 is as defined herein, and / or an optional further ring nitrogen R 9 The substituents are C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, and ring systems selected from the group consisting of phenyl rings, 5-6 membered heteroaryl rings and 3-6 membered heterocyclyl rings, said ring systems being selected from the group consisting of 0-5 R 16 m, R 4 , R 5 and R 16 is as defined herein.

[0048] In embodiments where at least one of X and Y is cyclopropyl, each R 8 is preferably, independently, oxo, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, amino, -NHC(O)CH3, hydroxyl, C1-C4 alkoxy, or C1-C4 alkylthio. More preferably, each R 8 are independently oxo, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, hydroxyl, C1-C4 alkoxy, or C1-C4 alkylthio, and most preferably each R 8 is independently halogen, or C1-C4 haloalkyl.

[0049] In embodiments where at least one of X and Y is cyclopropyl, each R 9 is preferably independently C1-C4 alkyl, C1-C4 haloalkyl, hydroxyl, C1-C4 alkoxy, or C1-C4 alkylthio.

[0050] In certain embodiments where at least one of X and Y is cyclopropyl and D is a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl ring as defined above, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, and 2-chloro-thiazo-5-yl, 2-chloro-3-pyridyl, 3-chloro-4-pyridyl, 1-methyl-3-(trifluoromethyl)-pyrazol-4-yl, thiazol-2-yl, thiazol-5-yl, pyrimidin-5-yl, 4-(tert-butoxy)phenyl, 2-chloro-4-pyridyl, 2-methyl-4-pyridyl, 2-trifluoro ... and 2-trifluoromethyl-3-pyridyl. In a subset of these embodiments, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, and 2-chloro-thiazo-5-yl, 2-chloro-3-pyridyl, 3-chloro-4-pyridyl, 1-methyl-3-(trifluoromethyl)-pyrazol-4-yl, thiazol-2-yl, thiazol-5-yl, pyrimidin-5-yl, 4-(tert-butoxy)phenyl, 2-chloro-4-pyridyl, 2-methyl-4-pyridyl, 2-trifluoromethyl-4-pyridyl, 4-pyridyl, thiophen-3-yl, 5-methyl-3-pyridyl, 5-methyl-2-pyridyl, 6-methyl-2-pyridyl, 3-trifluoromethyl-3-pyridyl, 2-fluoro-4-pyridyl, and 2-trifluoromethyl-3-pyridyl.In a further subset of these embodiments, D is selected from the group consisting of 4-chloro-3-pyridyl, 4-trifluoromethylpyridyl, 3-pyridyl, 2-fluoro-4-pyridyl, and 2-chloro-thiazo-5-yl (preferably, 2-fluoro-4-pyridyl).

[0051] When D is a phenyl ring Dp and is substituted, it is selected from 1 to 5 R 8 and thus has the structure [ka] wherein at least one R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 is other than hydrogen. 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 When at least one of R is not hydrogen, any remaining positions on the phenyl ring may be unsubstituted or, alternatively, may be represented by additional R 8 Those skilled in the art will recognize that Dp may carry a substituent, the position of which on the phenyl ring is indicated by the number in superscript p. When Dp is unsubstituted, R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 does not exist.

[0052] As mentioned above, R 8 The substitution of D with is determined by the presence or absence of cyclopropyl at positions X and / or Y. Thus, in Dp, where at least one of X and Y is cyclopropyl, R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5is preferably one or more independently selected from the group consisting of cyano, amino, C1-C3 dialkylamino, hydroxy, C1-C3 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, and halogen, and b is the point of attachment to the remainder of the molecule.

[0053] In one such set of embodiments, R 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 is independently selected from cyano, C1-C3 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen. 8p1 , R 8p2 , R 8p3 , R 8p4 and R 8p5 is independently selected from cyano, halogen (especially chloro or fluoro), methyl, methoxy, and trifluoromethyl.

[0054] In yet another set of embodiments, R 8p1 , R 8p2 , R 8p4 and R 8p5 Each of is non-existent and R 8p3 is cyano, C1-C3 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen. Preferably, in this set of embodiments, R 8p3 is halogen, more preferably chloro.

[0055] In a further set of embodiments, R 8p1 , R 8p4 and R 8p5 Each of is absent, and R 8p2 and R 8p3 are each independently cyano, C1-C3 alkyl, C1-C4 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, or halogen. In this set of embodiments, R 8p2 and R8p3 are each independently particularly preferably halogen, and R 8p2 and R 8p3 More preferably, both are chloro.

[0056] In one particularly preferred set of embodiments where at least one of X and / or Y is cyclopropyl, D is an unsubstituted phenyl ring.

[0057] In a further embodiment, a particularly preferred set of embodiments in which at least one of X and / or Y is cyclopropyl, D is selected from the group consisting of 4-chloro-phenyl, 4-trifluoromethyl-phenyl, 4-cyanophenyl, 4-fluoro-phenyl, 3,4-di-fluoro-phenyl, 2-trifluoromethyl-phenyl and 4-tolyl.

[0058] W acts as a linker moiety connecting ring D to the remainder of the molecule (i.e., to the phenyl-pyridazinone / phenyl-pyridazinedione moiety). Compounds of formula (I) where the linker is W1 are herbicidal, while compounds of formula (I) where the linker is W2 are not only herbicidal but may also be useful intermediates in the production of compounds of formula (I) bearing the W1 linker. Thus, in one set of embodiments, W is W1, while in a second set of embodiments, W is W2. In a third set of embodiments, W is -C≡C-.

[0059] Preferably, R 10 , R 11 , R 12 and R 13 are each independently selected from hydrogen or C1-C3 alkyl. In one set of embodiments, R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0060] Preferably, R 14 and R 15are each independently selected from hydrogen or C1-C3 alkyl. In one set of embodiments, R 14 and R 15 are both hydrogen.

[0061] Specific examples of W are -CH2-CH2-, -CH=CH-, cis [ka] and transformer [ka] and -C≡C-. In more preferred embodiments, W is -CH2-CH2-, or -CH=CH- (especially (E)-CH=CH-), more preferably also -CH2-CH2-.

[0062] In one preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl, ethyl, cyclopropyl, propargyl or C1 fluoroalkyl; R 2 is chloro, cyclopropyl, trifluoromethyl or methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro, chloro or C1-haloalkyl and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is hydrogen, chloro, fluoro, or bromo and is ortho relative to the -WD moiety; D is C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m-C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, -NR 4a R 5a , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3- C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino and C1-C6 haloalkoxy(C1-C6 alkyl)amino; or at least one R selected from the group consisting of a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring and a 3- to 6-membered heterocyclyl ring. 8 and the ring system is a phenyl ring substituted with 0 to 5 R 16 is replaced by; Any further R 8 The substituents may be selected from the group consisting of hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6-cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyl, and C2-C6 alkynyl; R 4 and R 5 are each independently hydrogen, C1-C3 alkyl, C1-C3 alkoxy, or C3-C6 cycloalkyl; m is an integer of 0, 1, or 2 (preferably, 0 or 2); Each R 4a and R 5a are independently selected from the group consisting of C1-C6 alkoxy and C3-C6 cycloalkyl, or R 4a and R 5a can be taken together to form a morpholinyl ring; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0063] In a more preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is one or two R 8 and at least one R 8 is C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m-C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, -S(O)2NHC(O)C1~C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino- and C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0 to 5 R 16 is replaced by; Any further R 8 The substituents may be selected from the group consisting of halogen, C1-C6 alkyl, and C1-C6 haloalkyl; R 4 and R 5 are each independently hydrogen, C1-C3 alkyl, C1-C3 alkoxy, or C3-C6 cycloalkyl; m is 0 or 2 (preferably 0); Each R 16 are independently halogen, cyano, C1-C4 alkyl, C1-C3 haloalkyl, or C1-C4 alkoxy; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0064] In an even more preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -S(O)2NHC(O)C1~C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl and -C(O)NR 4 R 5 or one R selected from the group consisting of a ring system selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl rings; 8 and the ring system is a phenyl ring substituted with 0-2 R 16 is replaced by; R 4 and R 5 are each independently hydrogen or C1-C3 alkyl; m is 0 or 2 (preferably 0); Each R16 are independently halogen or C1-C4 alkyl (preferably methyl); W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen

[0065] Yet in an even more preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is one R selected from the group consisting of methylsulfanylmethyl, isopropylsulfanylmethyl, sulfamoyl, methylsulfamoyl, and carbamoyl; or a ring system selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, 1,2,4-triazolyl, oxazolyl, and thiazolyl rings. 8 and the ring system is a phenyl ring substituted with 0-2 R 16 is replaced by; Each R 16 is methyl; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0066] In an alternative preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1is methyl, ethyl, cyclopropyl, propargyl or C1 fluoroalkyl; R 2 is chloro, cyclopropyl, trifluoromethyl or methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro, chloro or C1-haloalkyl and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is hydrogen, chloro, fluoro, or bromo and is ortho relative to the -WD moiety; D is C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, cyano-C1~C6-alkyl-, NR 4a R 5a , -C(S)NR 4 R 5 , -S(O)2NHC(O)C1-C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5, C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino-, C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 alkylsulfonylamino-, C1-C6 alkylsulfonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylsulfonylamino-, C1-C6 haloalkylsulfonyl(C1-C6 alkyl)amino-, C3-C6 cycloalkylsulfonylamino-, C3- at least one R selected from the group consisting of C6 cycloalkylsulfonyl(C1-C6 alkyl)amino-, hydroxyamino-, hydroxy(C1-C6 alkyl)amino, C1-C6 alkoxyamino, C1-C6 alkoxy(C1-C6 alkyl)amino, C1-C6 haloalkoxyamino, C1-C6 haloalkoxy(C1-C6 alkyl)amino; and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring; 8 and wherein the ring system is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with 0 to 5 R 16 is replaced by; Any further R 8 The substituents may be selected from the group consisting of hydroxyl, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6-cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyl, and C2-C6 alkynyl; and / or D is selected from the group consisting of C5-C6 alkyl, C5-C6 haloalkyl, C3-C6-cycloalkyl, C1-C3 alkoxy-C3 alkyl-, C3 alkoxy-C1-C2 alkyl-, C1-C3 haloalkoxy-C1-C3 alkyl-, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl-, C1-C6 hydroxyalkyl-, -C1-C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) mAt least one R selected from the group consisting of -C3-C6 cycloalkyl, cyano-C1-C6-alkyl-, and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring. 9 and the ring system is substituted with 0 to 5 R 16 is replaced by; R 4 and R 5 are each independently hydrogen, C1-C3 alkyl, C1-C3 alkoxy, or C3-C6 cycloalkyl; m is an integer of 0, 1, or 2 (preferably, 0 or 2); Each R 4a and R 5a are independently selected from the group consisting of C1-C6 alkoxy and C3-C6 cycloalkyl, or R 4a and R 5a can be taken together to form a morpholinyl ring; Each R 16 are independently halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, or C1-C6 haloalkoxy; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0067] In an alternative more preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is one or two R on a ring carbon. 8 and R is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with at least one R 8 is C1-C6 haloalkylcarbonyl-, C3-C6 cycloalkylcarbonyl-, -S(O) m -C1~C6 haloalkyl, -S(O) m -C3~C6 cycloalkyl, -OS(O)2C1~C3 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m -C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m -C3~C6 cycloalkyl, -S(O)2NHC(O)C1~C3 alkyl, -S(O)2NR 4 R 5 , -C(O)OH, -C(O)OC1-C6 alkyl, -C(O)NHS-(O)2C1-C6 alkyl, -C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C1-C6 alkylcarbonyl(C1-C6 alkyl)amino-, C1-C6 haloalkylcarbonylamino- and C1-C6 haloalkylcarbonyl(C1-C6 alkyl)amino-; or a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0 to 5 R 16 is replaced by; Any further R 8 The substituents may be selected from the group consisting of halogen, C1-C6 alkyl and C1-C6 haloalkyl; and / or D is selected from the group consisting of C5-C6 alkyl, C5-C6 haloalkyl, C3-C6-cycloalkyl, -C1-C3 alkyl-S(O) on the ring nitrogen. m -C1~C6 alkyl, -C1~C3 alkyl-S(O) m-C1~C6 haloalkyl, -C1~C3 alkyl-S(O) m - one R selected from the group consisting of C3-C6 cycloalkyl and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring; 9 and the ring system is substituted with 0 to 5 R 16 is replaced by; R 4 and R 5 are each independently hydrogen, C1-C3 alkyl, C1-C3 alkoxy, or C3-C6 cycloalkyl; m is 0 or 2 (preferably 0); Each R 16 are independently halogen, cyano, C1-C4 alkyl, C1-C3 haloalkyl, or C1-C4 alkoxy; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0068] In an alternative yet more preferred set of embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl, t-butyl, methyl, ethyl, propargyl, or methoxy; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is -C1-C3 alkyl-S(O) on the ring carbon. m -C1~C6 alkyl, -S(O)2NHC(O)C1~C3 alkyl, -S(O)2NR 4 R 5, -C(O)OH, -C(O)OC1-C6 alkyl and -C(O)NR 4 R 5 or one R selected from the group consisting of a ring system selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyridonyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, or 1,3,5-triazinyl rings; 8 and wherein the ring system is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 nitrogen atoms substituted with 0-2 R 16 and / or D is substituted on the ring nitrogen with one R selected from the group consisting of C5-C6 alkyl, C3-C6 cycloalkyl, and ring systems selected from the group consisting of phenyl rings, 5-6 membered heteroaryl rings, and 3-6 membered heterocyclyl rings. 9 and the ring system is substituted with 0 to 2 R 16 is replaced by; R 4 and R 5 are each independently hydrogen or C1-C3 alkyl; m is 0 or 2 (preferably 0); Each R 16 are independently halogen or C1-C4 alkyl (preferably methyl); W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0069] Yet another even more preferred set of alternative embodiments in compounds of formula (I) where both X and Y are other than cyclopropyl; R 1 is methyl; R 2 is methyl; G is hydrogen or -C(O)-R 3 and R 3 is isopropyl; X is fluoro and is ortho relative to the pyridazinone / pyridazinedione moiety; Y is chloro and is ortho relative to the -WD moiety; D is one R selected from the group consisting of methylsulfanylmethyl, isopropylsulfanylmethyl, sulfamoyl, methylsulfamoyl, and carbamoyl on a ring carbon; or a ring system selected from the group consisting of phenyl, morpholinyl, tetrahydrofuranyl, furyl, thienyl, pyrrolyl, pyrazolyl, 1,2,4-triazolyl, oxazolyl, and thiazolyl rings. 8 and the ring system is substituted with 0 to 2 R 16 and / or D is substituted on the ring nitrogen with one R selected from cyclopropyl or phenyl. 9 is replaced by; Each R 16 is methyl; W is W1; R 10 , R 11 , R 12 , and R 13 are all hydrogen.

[0070] The following Tables A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, C-1, C-2, C-3, and C-4 illustrate specific examples of the compound of formula (I) of the present invention.

[0071] Herbicidal Compounds of the Invention The numbering system used to describe the positions of X and Y in the compounds of formula (I) shown below is presented for clarity purposes only. [ka]

[0072] Table A-1 provides 672 compounds A-1.001 to A-1.672 of formula (I), where G is -H, W is -CH-CH-, R 1 , R 2 , X, Y, and D are as defined for compound numbers 1.001 to 1.672 in Table 1 below, respectively.

[0073] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11] [Table 1-12] [Table 1-13] [Table 1-14] [Table 1-15] [Table 1-16] [Table 1-17] [Table 1-18] [Table 1-19] [Table 1-20] [Table 1-21] [Table 1-22] [Table 1-23] [Table 1-24] [Table 1-25] [Table 1-26]

[0074] Table A-2 provides 672 compounds A-2.001 to A-2.672 of formula (I), where G is H, W is (E)-CH=CH-, and R 1 , R 2, X, Y, and D are as defined for compound numbers 1.001 to 1.672 in Table 1 above, respectively.

[0075] Table A-3 provides 672 compounds A-3.001 to A-3.672 of formula (I), where G is -(C=O)iPr, W is -CH2-CH2-, and R 1 , R 2 , X, Y, and D are as defined for compound numbers 1.001 to 1.672 in Table 1 above, respectively.

[0076] Table A-4 provides 672 compounds A-4.001 to A-4.672 of formula (I), where G is -(C=O)iPr, W is (E)-CH=CH-, and R 1 , R 2 , X, Y, and D are as defined for compound numbers 1.001 to 1.672 in Table 1 above, respectively.

[0077] Table B-1 provides 744 compounds B-1.001 to B-1.744 of formula (I), where G is -H, W is -CH-CH-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744, respectively, in Table 2 below.

[0078] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4] [Table 2-5]

Table 2-6

Table 2-7

Table 2-8

Table 2-9

Table 2-10

Table 2-11

Table 2-12

Table 2-13

Table 2-14

Table 2-15

Table 2-16

Table 2-17

Table 2-18

Table 2-19

Table 2-20

Table 2-21

Table 2-22

[0079] Table B-2 provides 744 compounds B-2.001 to B-2.744 of formula (I), where G is -H, W is (E)-CH=CH-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744, respectively, in Table 2 above.

[0080] Table B-3 provides 744 compounds B-3.001 to B-3.744 of formula (I), where G is -(C=O)iPr, W is -CH2-CH2-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744, respectively, in Table 2 above.

[0081] Table B-4 provides 744 compounds B-4.001 to B-4.744 of formula (I), where G is -(C=O)iPr, W is (E)-CH=CH-, X is 6-cyclopropyl, and R 1 , R 2 , Y, and D are as defined for compound numbers 2.001 to 2.744, respectively, in Table 2 above.

[0082] Table C-1 provides 744 compounds C-1.001 to C-1.744 of formula (I), in which G is -H, W is -CH-CH-, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744, respectively, in Table 3 below.

[0083]

Table 3-1

Table 3-2

Table 3-3

Table 3-4

Table 3-5

Table 3-6

Table 3-7

Table 3-8

Table 3-9

Table 3-10

Table 3-11

Table 3-12

Table 3-13

Table 3-14

Table 3-15

Table 3-16

Table 3-17

[0084] Table C-2 provides 744 compounds C-2.001 to C-2.744 of formula (I), in which G is -H, W is (E)-CH=CH-, Y is 3-cyclopropyl, and R 1 , R 2 , X, Y, and D are as defined for compound numbers 3.001 to 3.744, respectively, in Table 3 above.

[0085] Table C-3 provides 744 compounds C-3.001 to C-3.744 of formula (I), in which G is -(C=O)iPr, W is -CH2-CH2-, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744, respectively, in Table 3 above.

[0086] Table C-4 provides 744 compounds C-4.001 to C-4.744 of formula (I), in which G is -(C=O)iPr, W is (E)-CH=CH-, Y is 3-cyclopropyl, and R 1 , R 2 , X, and D are as defined for compound numbers 3.001 to 3.744, respectively, in Table 3 above.

[0087] The compounds of the present invention may be prepared according to the following scheme, in which the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , W, D, Dp, G, X, Y, and m have the definitions set forth herein above (unless expressly stated otherwise).

[0088] Certain compounds (I-ii) of the present invention may be prepared from compound (2) as shown in Reaction Scheme 1. Compound (I-ii) is a compound of formula (I) where W is -CH-CH-.

[0089] Reaction Scheme 1 [ka] Compound (I-ii) can be prepared by catalytic hydrogenation of compound (2) with hydrogen gas in a suitable solvent (e.g., tetrahydrofuran, methanol, ethanol, acetic acid or ethyl acetate) in the presence of a suitable catalyst (e.g., Pd / C, Pd / CaCO3, Rh / Al2CO3 or sponge nickel) at a temperature of -10 to 100°C.

[0090] Alternatively, compound (I-ii) may also be prepared by catalytic transfer hydrogenation of compound (2) by treatment with a suitable hydrogen source in a suitable solvent in the presence of a suitable catalyst at temperatures between −10 and 100° C. Examples of suitable systems are tetrahydroxydiboron in dichloromethane / water or dichloromethane / methanol mixtures in the presence of Pd / C, Pd(OAc) 2 or Pd(OH) 2 / C (J. Am. Chem. Soc., 2016, 138, 6107-6110), or diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate in ethanol in the presence of Pd / C (Tetrahedron Letters, 2009, 50, 1026).

[0091] Compound (2) can be prepared from compound (3) and compound (4) as shown in Reaction Scheme 2 according to the Suzuki or Heck Protocol below. When using the Suzuki Protocol, compound (4) is an organoboron compound, such as a boronic acid, a boronic ester, or potassium trifluoroborate. When using the Heck Protocol, compound (4) is a styrene.

[0092] Alternatively, compound (I-ii) may also be prepared by reduction with a diimide generated in situ from a suitable precursor in a suitable solvent at a temperature of -10 to 200°C. Examples of suitable reagents for the generation of diimides include substituted arylsulfonyl hydrazides, such as 2,4,6-triisopropylbenzenesulfonyl hydrazide, optionally in the presence of a suitable base. Examples of suitable bases include triethylamine, diisopropylethylamine, potassium carbonate and sodium carbonate. Suitable solvents include tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetonitrile and dimethylformamide.

[0093] Reaction Scheme 2 [ka] Suzuki Protocol Compound (2) may be prepared by treatment of compound (3) and compound (4) in the presence of a suitable base and a suitable catalyst in a suitable solvent at a temperature between 10 and 150°C. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, sodium bicarbonate, and potassium fluoride. Examples of suitable catalysts include 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf)·DCM], tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], and a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine. Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. Many compounds (4) are commercially available [e.g., trans-2-(4-biphenyl)vinylboronic acid] or can be made by known methods. An example of a compound (3) that has particular utility in the Suzuki protocol is the isobutyryl ester (3-i), where G is isobutyryl.

[0094] Those skilled in the art will recognize that the conditions of the Suzuki Protocol tend to cleave ester groups, and as a result, Reaction Scheme 2 can also describe reactions in which the starting material (3) contains an ester moiety [such that G is an acyl group], but the product (2) does not contain an ester moiety [such that G is hydrogen].

[0095] Heck Protocol Compound (2) can be prepared by treatment of compound (3) and compound (4) in the presence of a suitable base and a suitable catalyst at a temperature of 10 to 150°C. An additional solvent may be optionally included. Examples of suitable bases include triethylamine, morpholine, N-methylmorpholine, diisopropylethylamine and pyridine. Examples of suitable catalysts include tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, and a palladacycle precatalyst, such as a catalyst system formed in situ from chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II). Examples of optional additional solvents include 1,4-dioxane, tetrahydrofuran, acetonitrile and toluene. Many compounds (4) are commercially available [e.g., 4-cyanostyrene] or can be made by known methods. An example of a compound (3) that has particular utility in the Heck protocol is the isobutyryl ester (3-i), where G is isobutyryl.

[0096] Compound (3-i) can be prepared from compound (5) as shown in Reaction Scheme 3.

[0097] Reaction Scheme 3 [ka] Compound (3-i) may be prepared by treatment of compound (5) and isobutyryl chloride in a suitable solvent (e.g., dichloromethane, acetonitrile, or toluene) in the presence of a suitable base (e.g., triethylamine, diisopropylethylamine, or pyridine) at a temperature of −10 to 60° C. A catalyst (e.g., 4-(dimethylamino)pyridine) may optionally be included.

[0098] Compound (5) can be prepared from compound (6) as shown in Reaction Scheme 4 by heating compound (6) with a base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hexamethyldisilazide or lithium hexamethyldisilazide) in a solvent (e.g., acetonitrile, N,N-dimethylformamide or toluene) at a temperature between 50 and 200° C. Conventional heating or microwave heating can be used.

[0099] Reaction Scheme 4 [ka] Compound (6) can be prepared from phenylacetic acid (7) as shown in Reaction Scheme 5.

[0100] Reaction Scheme 5 [ka] With reference to Reaction Scheme 5, an example of hydrazine (8) is methylhydrazine, and an example of ketoester (10) is ethyl pyruvate. An example of hydrazone (9) is ethyl (2E / Z)-2-(methylhydrazono)propanoate, prepared by the method described in WO 2016 / 008816. An example of phenylacetic acid (7) is (2-bromo-6-fluoro-phenyl)acetic acid, which may be synthesized according to Reaction Scheme 10. A further example of phenylacetic acid (7) is (2-bromo-3-chloro-6-fluoro-phenyl)acetic acid, which may be synthesized according to Reaction Scheme 11.

[0101] Certain compounds of the invention, (I-iii), may be prepared from compound (11), as shown in Reaction Scheme 6, or from compound (I-iv), as shown in Reaction Scheme 12. Compound (I-iii) is a compound of formula (I), where W is -CH-CH- and G is hydrogen.

[0102] Reaction Scheme 6 [ka] Compound (I-iii) may be prepared by heating compound (11) with a base (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hexamethyldisilazide or lithium hexamethyldisilazide) in a solvent (e.g., acetonitrile, N,N-dimethylformamide or toluene) at a temperature between 50 and 200° C. Conventional or microwave heating may be used.

[0103] Compound (11) can be prepared from compound (12) as shown in Reaction Scheme 7 below.

[0104] Reaction Scheme 7 [ka] Compound (12) can be prepared from compound (13) as shown in Reaction Scheme 8. Many compounds (13) are commercially available [e.g., methyl 2-phenylacetate and methyl 2-(2-fluorophenyl)acetate].

[0105] With reference to Reaction Scheme 8, the phosphorane (15) can be made according to Reaction Scheme 9.

[0106] Reaction Scheme 8 [ka] Reaction Scheme 9 [ka] With reference to Reaction Scheme 9, examples of suitable bases are sodium hydride, sodium hexamethyldisilazide, and potassium tert-butoxide. Compound (16) is an electrophile where LG is a leaving group [e.g., chloride, bromide, iodide, tosylate, or mesylate]. Many compounds (16) are commercially available [e.g., 4-chlorobenzyl bromide or 2-chloro-5-chloromethylthiazole].

[0107] Reaction Scheme 10 [ka] With reference to Reaction Scheme 10, (2-bromo-6-fluoro-phenyl)acetic acid ethyl ester can be prepared as described in Lundgren et al. JACS 2016, 138, 13826-13829.

[0108] Reaction Scheme 11 [ka] With reference to Reaction Scheme 11, 2-bromo-1-chloro-4-fluoro-benzene is commercially available.

[0109] Reaction Scheme 12 [ka] Compound (I-iii) may be prepared by treating compound (I-iv) with a metal hydroxide (e.g., sodium hydroxide, lithium hydroxide, or potassium hydroxide) in a mixture of water and a suitable solvent (e.g., methanol, ethanol, or tetrahydrofuran) at a temperature between 0° C. and 100° C.; or by treating compound (I-iv) with a metal carbonate (e.g., sodium carbonate or potassium carbonate) in an alcohol solvent (e.g., methanol or ethanol). Compound (I-iv) is a compound of formula (I), where W is -CH2-CH2- and G is C(O)R. 3 It is.

[0110] Compound (2) can be prepared from compounds (14) and (15) as shown in Reaction Scheme 13 by the Suzuki Protocol or the Heck Protocol described below. When using the Suzuki Protocol, compound (14) is an organoboron compound, such as a boronic acid, a boronic ester, or a potassium trifluoroborate salt, and compound (15) is a halide or pseudohalide compound, such as a chloride, bromide, iodide, or triflate. When using the Heck Protocol, compound (14) is a styrene, and compound (15) is a halide or pseudohalide compound, such as a chloride, bromide, iodide, or triflate.

[0111] Reaction Scheme 13 [ka] Suzuki Protocol Compound (2) may be prepared by treatment of compound (14) and compound (15) in the presence of a suitable base and a suitable catalyst in a suitable solvent at a temperature between 10 and 150°C. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, sodium bicarbonate and potassium fluoride. Examples of suitable catalysts include 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf)·DCM], tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], and the catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine. Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile and toluene. Many compounds (15) are commercially available or can be made by known methods. An example of a compound (14) that has particular utility in the Suzuki protocol is the isobutyryl ester (14-i), where G is isobutyryl.

[0112] Those skilled in the art will recognize that the conditions of the Suzuki protocol tend to cleave ester groups, and as a result, Reaction Scheme 13 can also describe reactions in which starting material (14) contains an ester moiety [such that G is an acyl group], but product (2) does not contain an ester moiety [such that G is hydrogen].

[0113] Heck Protocol Compound (2) can be prepared by treating compound (14) with compound (15) in the presence of a suitable base and a suitable catalyst at a temperature of 10 to 150° C. An additional solvent can be optionally included. Examples of suitable bases include triethylamine, morpholine, N-methylmorpholine, diisopropylethylamine and pyridine. Examples of suitable catalysts include tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, and a palladacycle precatalyst, such as a catalyst system formed in situ from chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II). Examples of optional additional solvents include 1,4-dioxane, tetrahydrofuran, acetonitrile and toluene. Many compounds (15) are commercially available or can be made by known methods. An example of a compound (14) that has particular utility in the Heck protocol is the isobutyryl ester (14-i), where G is isobutyryl.

[0114] Compound (14-ii), where J is an organoboron species, such as a boronic ester, can be prepared from compound (3) and compound (16) as shown in Reaction Scheme 14.

[0115] Reaction Scheme 14 [ka] Compound (14-ii) may be prepared by treatment of compound (3) and compound (16) in the presence of a suitable base and a suitable catalyst at a temperature between 10 and 150°C. An additional solvent may be optionally included. Examples of suitable bases include triethylamine, morpholine, N-methylmorpholine, diisopropylethylamine and pyridine. Examples of suitable catalysts are tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, and a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate. Examples of optional additional solvents include 1,4-dioxane, tetrahydrofuran, acetonitrile and toluene. Many compounds (16) are commercially available (e.g., vinylboronic acid MIDA ester or vinylboronic acid pinacol ester) or can be made by known methods. An example of a compound (3) that has particular utility in the Heck protocol is the isobutyryl ester (3-i), where G is isobutyryl.

[0116] Compound (14-iii), where J is hydrogen, can be prepared from compound (3) as shown in Reaction Scheme 15.

[0117] Reaction Scheme 15 [ka] Compound (14-iii) may be prepared by treatment of compound (3) with tributyl(vinyl)stannane in a suitable solvent, optionally in the presence of a suitable base and in the presence of a suitable catalyst, at a temperature between 10 and 150° C. Examples of optional bases include triethylamine, morpholine, N-methylmorpholine, diisopropylethylamine, and pyridine. Examples of suitable catalysts include 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf)·DCM], tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], a catalyst system formed in situ from a mixture of palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, and a catalyst system formed in situ from a palladacycle catalyst precursor, such as chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II). Examples of suitable solvents include 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. An example of a compound (3) having particular utility is the isobutyryl ester (3-i), where G is isobutyryl.

[0118] Compound (18) can be prepared from compound (3) via the Sonogashira reaction as shown in Reaction Scheme 16.

[0119] Reaction Scheme 16 [ka] Compound (18) can be prepared by treating compound (3) and compound (17) in the presence of a suitable base and a suitable catalyst at a temperature of 10 to 150°C. Optionally, an additional solvent may be added. Examples of suitable bases include triethylamine, morpholine, N-methylmorpholine, diisopropylamine, diisopropylethylamine and pyridine. Examples of suitable catalysts include a catalyst system formed in situ from a mixture of bis(triphenylphosphine)palladium(II) dichloride [Pd(PPh3)Cl2], palladium(II) acetate and triphenylphosphine, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, and a catalyst system formed in situ from a palladacycle catalyst precursor, such as chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II). Optionally, a copper catalyst, such as copper(I) iodide, may also be added. Examples of suitable additional solvents are 1,4-dioxane, tetrahydrofuran, acetonitrile, toluene and N,N-dimethylformamide. An example of a compound (3) having particular utility is the isobutyryl ester (3-i), where G is isobutyryl.

[0120] Those skilled in the art will recognize that the conditions for the Sonogashira reaction tend to cleave ester groups, and as a result, Reaction Scheme 16 can also describe a reaction in which starting material (3) contains an ester moiety [such that G is an acyl group], but product (18) does not contain an ester moiety [such that G is hydrogen].

[0121] Compound (19) can be prepared via a Suzuki reaction from compound (3) and compound (20), as shown in Reaction Scheme 17, where compound (20) is a suitable organoboron species, such as a boronic acid, a boronic ester, or potassium trifluoroborate.

[0122] Reaction Scheme 17 [ka] Compound (19) may be prepared by treatment of compound (3) and compound (20) in the presence of a suitable base and a suitable catalyst in a suitable solvent at a temperature between 10 and 150° C. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, sodium bicarbonate, and potassium fluoride. Examples of suitable catalysts include 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane complex [PdCl2(dppf)·DCM], a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphonium tetrafluoroborate, a catalyst system formed in situ from a mixture of tris(dibenzylideneacetone)dipalladium(0) and tricyclohexylphosphine, a catalyst system formed in situ from a palladacycle catalyst precursor, such as chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II), and a catalyst system formed in situ from a palladacycle catalyst precursor, such as chloro[(tricyclohexylphosphine)-2-(2'-aminobiphenyl)]palladium(II). Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. Some compounds (20) are commercially available [e.g., 4,4,5,5-tetramethyl-2-(2-phenyl-cyclopropyl)-[1,3,2]dioxaborolane] or can be made by known methods (see, for example, the methods described in Org. Process Res. Dev. 2012, 16, 87-95). An example of a compound (3) that has particular utility in the Suzuki reaction is the benzyl ether (3-ii), where G is benzyl.

[0123] Reaction Scheme 18 [ka] Compound (I9-ii) can be prepared by catalytic hydrogenation of compound (19-i) with hydrogen gas in a suitable solvent (e.g., tetrahydrofuran, methanol, ethanol, acetic acid or ethyl acetate) in the presence of a suitable catalyst (e.g., Pd / C, Pd / CaCO3, Rh / Al2CO3 or sponge nickel) at a temperature of -10 to 100°C.

[0124] Certain compounds of the invention (I-ii) may be prepared from compound (21) as shown in Reaction Scheme 19. Compound (I-ii) is a compound of formula (I) where W is -CH-CH-.

[0125] Reaction Scheme 19 [ka] Compounds (I-ii) may be prepared by treatment of compound (21) (where [B] may be a trialkylborane, an alkylboronic acid, an alkylboronic ester, or an alkylpotassium trifluoroborate) with compound (15) in the presence of a suitable base and a suitable catalyst in a suitable solvent at a temperature between 10 and 150° C. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, cesium carbonate, sodium bicarbonate, and potassium fluoride. Examples of suitable catalysts include 1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM], [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)dichloropalladium(II) [Pd-PEPPSI™-IPent], palladacycle precatalysts in In situ formed catalytic systems, such as chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) [RuPhos-Pd-G2], [dicyclohexyl[2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine](methanesulfonyl)phosphine, Examples of suitable solvents include (4-(N,N-dimethylamino)phenyl)di-tert-butylphosphine](methanesulfonato-κO)[2'-(methylamino-κN)[1,1'-biphenyl]-2-yl-κC]palladium [XPhos-Pd-G4], and [(4-(N,N-dimethylamino)phenyl)di-tert-butylphosphine](methanesulfonato-κO)[2'-(methylamino-κN)[1,1'-biphenyl]-2-yl-κC]palladium [APhos-Pd-G4]. Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. Many compounds (15) are commercially available or can be made by known methods. An example of compound (21) that has particular utility in the Suzuki protocol is the isobutyryl ester (21-i), where G is isobutyryl.

[0126] Those skilled in the art will recognize that the conditions of the Suzuki protocol tend to cleave ester groups, and as a result, Reaction Scheme 19 can also describe reactions in which the starting material (21) contains an ester moiety [such that G is an acyl group], but the product (I-ii) does not contain an ester moiety [such that G is hydrogen].

[0127] Reaction Scheme 20 [ka] Compounds (21) can be prepared by hydroboration of alkenes (14-iii) using a suitable hydroboration reagent (22) in a suitable solvent with the optional addition of a suitable catalyst at temperatures between 0° C. and 100° C. Examples of hydroboration reagents include borane, dichloroborane, dibromoborane, 4,4,5,5-tetramethyl-1,3,2-dioxaborolane [pinacolborane], 1,3,2-benzodioxaborole [catecholborane] or 9-borylbicyclo[3.3.1]nonane [9-BBN]. Examples of suitable solvents include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 2-methoxy-2-methyl-propane [MTBE] and diethyl ether. An example of a suitable catalyst includes the catalyst system formed in situ from bis(1,5-cyclooctadiene)diiridium(I) dichloride [[Ir(COD)Cl]2] and 4-diphenylphosphanylbutyl(diphenyl)phosphane [DPPB] [J. Am. Chem. Soc., 2004, 126, 9200-9201].

[0128] When [B] is an alkylboronic acid ester, it can be converted to the corresponding boronic acid by treatment with methylboronic acid [MeB(OH)2] and trifluoroacetic acid in a suitable solvent, such as dichloromethane [DCM], at a temperature between 0 and 40° C. [Org. Lett., 2019, 21, 3048-3052]. When [B] is an alkylboronic acid or ester, it can be converted to the corresponding alkylpotassium trifluoroborate by treatment with potassium bifluoride in a suitable solvent, such as methanol or acetone, at a temperature between 0 and 40° C.

[0129] Reaction Scheme 21 [ka] Compound (I-iii), where Y is cyclopropyl, may be prepared by treatment of compound (Iv) with compound (23), where [B] may be trialkylborane, alkylboronic acid, alkylboronic ester, or alkylpotassium trifluoroborate, in the presence of a suitable base and a suitable catalyst in a suitable solvent at a temperature between 10 and 150° C. Compound (Iv) is a compound of formula (I), where C is —CH2—CH2— and G is C(o)R 3and Y is -Cl. Examples of suitable bases include potassium carbonate, potassium phosphate, sodium carbonate, cesium carbonate, sodium bicarbonate, and potassium fluoride. Examples of suitable catalysts include 1,1'-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM], [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)dichloropalladium(II) [Pd-PEPPSI™-IPent], palladacycle precatalysts in In situ formed catalytic systems, such as chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) [RuPhos-Pd-G2], [dicyclohexyl[2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine](methanesulfonyl)phosphine, Examples of suitable solvents include (4-(N,N-dimethylamino)phenyl)di-tert-butylphosphine](methanesulfonato-κO)[2'-(methylamino-κN)[1,1'-biphenyl]-2-yl-κC]palladium [XPhos-Pd-G4], and [(4-(N,N-dimethylamino)phenyl)di-tert-butylphosphine](methanesulfonato-κO)[2'-(methylamino-κN)[1,1'-biphenyl]-2-yl-κC]palladium [APhos-Pd-G4]. Examples of suitable solvents include water, 1,4-dioxane, tetrahydrofuran, acetonitrile, and toluene. An example of a compound (Iv) having particular utility in the Suzuki protocol is the isobutyryl ester (Iv), where G is isobutyryl.

[0130] Those skilled in the art will recognize that the conditions of the Suzuki Protocol tend to cleave ester groups, and as a result, Reaction Scheme 21 can describe a reaction in which the starting material (Iv) contains an ester moiety [such that G is an acyl group], but the product (I-iii) does not contain an ester moiety [such that G is hydrogen].

[0131] The compounds of formula (I) according to the present invention can be used as herbicides themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surfactants (SFA).Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the preceding claims and an agriculturally acceptable formulation adjuvant.The composition may be in the form of a concentrate that is diluted before use, but ready-to-use compositions can also be made.Final dilution is usually with water, but instead of or in addition to water, it can be with, for example, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0132] The herbicidal compositions generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of a compound of formula I and preferably 1 to 99.9% by weight of a formulation adjuvant which comprises 0 to 25% by weight of a surface-active substance.

[0133] The compositions can be selected from several formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dispersible powders (DP), soluble powders (SP), water-soluble granules (SG), water-dispersible granules (WG), wettable powders (WP), granules (GR) (sustained or rapid release), soluble concentrates (SL), oil-miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil-in-water (EW) and water-in-oil (EO)), microemulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The formulation type selected will in any case depend on the specific purpose envisaged, as well as the physical, chemical and biological properties of the compound of formula (I).

[0134] Dispersible Powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid excipients (e.g., natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomaceous earth, chalk, diatomaceous earth, calcium phosphate, calcium and magnesium carbonate, sulfur, lime, flour, talc, and other organic and inorganic solid carriers) and mechanically grinding the mixture into a fine powder.

[0135] Soluble powders (SP) can be prepared by mixing the compound of formula (I) with one or more water-soluble inorganic salts (e.g., sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (e.g., polysaccharides), and optionally one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility / solubility. The mixture is then ground into a fine powder. Similar compositions can also be granulated to form water-soluble granules (SG).

[0136] Wettable powders (WP) can be prepared by mixing a compound of formula (I) with one or more solid excipients or carriers, one or more wetting agents, and preferably one or more dispersing agents, and optionally one or more suspending agents to facilitate dispersion in a liquid. The mixture is then ground to a fine powder. Similar compositions can also be granulated to form water-dispersible granules (WG).

[0137] Granules (GR) can be formed by granulating a mixture of a compound of formula (I) and one or more powdered solid excipients or carriers, or by absorbing a compound of formula (I) (or its solution in a suitable agent) into a porous granular material (e.g., pumice, attapulgite clay, Fuller's earth, diatomaceous earth, diatomaceous earth or ground corn cob) from a preformed blank granule, or by adsorbing a compound of formula (I) (or its solution in a suitable agent) onto a hard core material (e.g., sand, silicates, mineral carbonates, mineral sulfates or mineral phosphates) and drying as required. Agents commonly used to aid absorption or adsorption include solvents (e.g., aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and binders (e.g., polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and vegetable oil). One or more other additives can also be included in the granule (e.g., emulsifiers, wetting agents or dispersing agents).

[0138] Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain surfactants (e.g. to improve water dilution or to prevent crystallization in the spray tank).

[0139] Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifiers or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (e.g., alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO100, SOLVESSO150 and SOLVESSO200; SOLVESSO is a registered trademark), ketones (e.g., cyclohexanone or methylcyclohexanone) and alcohols (e.g., benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (e.g., N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (e.g., C8-C10 alkyl esters, such as ethyl ketones, ...10 fatty acid dimethylamides) and chlorinated hydrocarbons. EC products emulsify spontaneously upon addition to water, producing emulsions with sufficient stability to allow spray application via appropriate equipment.

[0140] The preparation of an EW involves obtaining a compound of formula (I) as a liquid (if it is not liquid at room temperature, it may melt at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in a suitable solvent) and then emulsifying the resulting liquid or solution into water containing one or more SFAs under high shear to produce an emulsion. Suitable solvents for use in the EW include vegetable oils, chlorinated hydrocarbons (e.g., chlorobenzene), aromatic solvents (e.g., alkylbenzenes or alkylnaphthalenes) and other suitable organic solvents that have poor solubility in water.

[0141] Microemulsions (MEs) may be prepared by mixing water and a blend of one or more solvents with one or more SFAs, resulting in the spontaneous formation of a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in the water or in the solvent / SFA blend. Suitable solvents for use in MEs include those described above for use in ECs or EWs. MEs may be oil-in-water or water-in-oil systems (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. MEs may remain as microemulsions or form regular oil-in-water emulsions, suitable for dilution into water.

[0142] Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball milling or bead milling a solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and suspending agents may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water containing the above-mentioned agents to produce the desired end product.

[0143] Aerosol formulations include a compound of formula (I) and a suitable propellant (e.g., n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid, such as n-propanol) to provide a composition for use in a non-pressurized, manually operated spray pump.

[0144] Capsule suspensions (CS) can be prepared in a similar manner to the preparation of EW formulations, but with an additional polymerization step to obtain an aqueous dispersion of oil droplets, in which each oil droplet is encapsulated by a polymer shell and contains the compound of formula (I), and therefore optionally a carrier or excipient. The polymer shell can be produced by an interfacial polycondensation reaction or a coacervation procedure. The compositions can achieve a controlled release of the compound of formula (I), which can be used for seed treatment. The compound of formula (I) can also be formulated in a biodegradable polymer matrix to achieve a controlled sustained release of the compound.

[0145] The composition may include one or more additives that improve the biological performance of the composition, for example by improving wetting, retention or distribution on a surface, resistance to rain on the treated surface, or uptake or mobility of the compound of formula (I). Such additives include surface active agents (SFAs), spray additives based on oils, such as certain mineral oils or natural vegetable oils (e.g., soybean oil and rapeseed oil), and blends of these with other bioavailability enhancing adjuvants (ingredients that can assist or modify the action of the compound of formula (I)).

[0146] Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.

[0147] Suitable SFAs of the cationic type include quaternary ammonium compounds (eg cetyltrimethylammonium bromide), imidazolines and amine salts.

[0148] Suitable anionic SFAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate, and mixtures of sodium diisopropylnaphthalenesulfonate and sodium triisopropylnaphthalenesulfonate), ether sulfates, alcohol ether sulfates (e.g., sodium laureth-3-sulfate), ether carboxylates (e.g., sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), for example, between lauryl alcohol and tetraphosphoric acid; furthermore, these products may be ethoxylated), sulfosuccinamates, paraffins or sulfonated olefins, taurates and lignosulfonates.

[0149] Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

[0150] Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (e.g. oleyl alcohol or cetyl alcohol) or alkylphenols (e.g. octylphenol, nonylphenol or octylcresol); partial esters derived from long-chain fatty acids or from hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (containing ethylene oxide and propylene oxide); alkanolamides; simple esters (e.g. fatty acid polyethylene glycol esters); amine oxides (e.g. lauryl dimethylamine oxide); and lecithin.

[0151] Suitable suspending agents include hydrocolloids (eg polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (eg bentonite or attapulgite).

[0152] The composition of the present invention may further comprise at least one additional pesticide. For example, the compounds according to the present invention may also be used in combination with other herbicides or crop growth regulators. In a preferred embodiment, the additional pesticide is a herbicide and / or a safener for a herbicide. Specific examples of such mixtures are (where "I" represents a compound of formula (I)):-I+acetochlor;I+acifluorfen (including acifluorfen-sodium);I+aclonifen;I+ametryne;I+amicarbazone;I+aminopyralid;I+aminotriazole;I+atrazine;I+beflubutamid-M;I+benquitrione;I+bensulfuron (including bensulfuron-methyl);I+bentazon;I+bicyclopyrone;I+vilanaphos;I+bicyclopyrone ... Spirivac-sodium;I+Bixthrozone;I+Bromacil;I+Bromoxynil;I+Butachlor;I+Butafenacil;I+Carfentrazone (including Carfentrazone-ethyl);I+Cloransulam (including Cloransulam-methyl);I+Chlorimuron (including Chlorimuron-ethyl);I+Chlorotoluron;I+Chlorsulfuron;I+Cinmethylin;I+Cracifos;I+Clethodim;I+Clodinafop (including Clodinafop-propargyl) I+Clomazone;I+Clopyralid;I+Cyclopyranyl;I+Cyclopyrimorate;I+Cyclosulfamuron;I+Cyhalofop (including cyhalofop butyl);I+2,4-D (including its choline salt and its 2-ethylhexyl ester);I+2,4-DB;I+Desmedipham;I+Dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, I+diclosulam;I+diflufenican;I+diflufenzopyr;I+dimethachlor;I+dimethenamid-P;I+diquat dibromide;I+diuron;I+epirifenacil;I+ethalfluralin;I+ethofumesate;I+fenoxaprop (including fenoxaprop-P-ethyl);I+fenoxasulfone;I+fenquinotrione;I+fentrazamide;I+flazasulfuron;I+florasulam;I+Florpyrauxifen (including florpyrauxifen-benzyl); I+Fluazifop (including fluazifop-p-butyl); I+Flucarbazone (including flucarbazone-sodium); I+Flufenacet; I+Flumetsulam; I+Flumioxazin; I+Fluometuron; I+Flupyrsulfuron (including flupyrsulfuron-methyl-sodium); I+Fluroxypyr (including fluroxypyr-meptyl); I+Fomesafen; I+Foramsulfuron; I+Glufosinate (including its ammonium salt); I+ Glyphosate (including its diammonium, isopropylammonium and potassium salts); I+ Halauxifen (including halauxifen-methyl); I+ Haloxyfop (including haloxyfop-methyl); I+ Hexazinone; I+ Hydantocidin; I+ Imazamox; I+ Imazapic; I+ Imazapyr; I+ Imazethapyr; I+ Indaziflam; I+ Iodosulfuron (including iodosulfuron-methyl-sodium); I+ Iofensulfuron (including iofensulfuron-sodium); I+ Ioxynil; I +Isoproturon;I+Isoxaflutole;I+Lancotrione;I+MCPA;I+MCPB;I+Mecoprop-P;I+Mesosulfuron (including mesosulfuron-methyl);I+Mesotrione;I+Metamitron;I+Metazachlor;I+Methiozoline;I+Metolachlor;I+Metosulam;I+Metribuzin;I+Metsulfuron;I+Napropamide;I+Nicosulfuron;I+Norflurazon;I+Oxadiazon;I+Oxasulfuron;I+Oxyfluorfen;I+Paraquat dichloride;I+Pendimethalin;I+ Penoxulam;I+Phenmedipham;I+Picloram;I+Pinoxaden;I+Pretilachlor;I+Primisulfuron-methyl;I+Prometryn;I+Propanil;I+Propaquizafop;I+Propyrisulfuron;I+Propyzamide;I+Prosulfocarb;I+Prosulfuron;I+Pyraclonil;I+Pyraflufen (including pyraflufen-ethyl);I+Pyrasulfotole;I+Pyridate;I+Pyriftalid;I+Pyrimisulfan;I+Pyroxasulfone;I+Pyroxulam;I+Quinclorac;I+Quinmerac;I+Quizalofop (including Quizalofop-P-ethyl and Quizalofop-P-tefuryl);I+Rimsulfuron;I+Saflufenacil;I+Sethoxydim;I+Simazine;I+S-Metallochlor;I+Sulfentrazone;I+Sulfosulfuron;I+Tebuthiuron;I+Tefuryltrione;I+Tembotrione;I+Terbuthylazine;I+Terbutryne;I+Tetflupyrrolimeth;I+Thiencarbazone;I+Thiefensulfuron;I+Thiafenacil;I+Torpyralate;I+Topramezone;I+Tralkoxydim;I+Triafamone;I+To lyasulfuron;I+triasulfuron;I+tribenuron (including tribenuron-methyl);I+triclopyr;I+trifloxysulfuron (including trifloxysulfuron-sodium);I+trifludimoxadine;I+trifluralin;I+triflusulfuron;I+3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester;I+4-hydroxy -1-Methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;I+4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;I+5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;I+4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one;I+4-hydroxy-1,5-dimethyl-3-[1-methyl-5 -(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one;I+(4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one;I+3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione;I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione;I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione;I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione;I+6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione;I+2-[2-(3, 4-Dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione;I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione;I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione;I+3-[6-cyclopropyl- 2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione;I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione;I+6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione;I+2-[ 6-Cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione;I+4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione;I+4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione;I+4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (or its agrochemically acceptable esters, such as methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2 -carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate;I+3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide;I+3-(isopropylsulfanylmethyl)-N-(5-methyl-1, 3,4-Oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide;I+3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide;I+3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide xadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide;I+ethyl 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate;I+6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one;I+1-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-4,4,4-trifluoro-butan-1-one and I+5-[2-chloro-6-(5-chloropyrimidin-2-yl)oxy-phenyl]-3-(difluoromethyl)isoxazole. The mixing partners of the compounds of formula (I) may also be in the form of esters or salts, as for example mentioned in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0153] The compounds of formula (I) may also be used in mixtures with other pesticides, such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

[0154] The mixing ratio of the compound of formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0155] Mixtures may be advantageously used in the abovementioned formulations (in which case "active ingredient" relates to the respective mixture of the compound of formula (I) with the mixing partner).

[0156] The compound of formula (I) of the present invention may also be combined with herbicide safeners.Preferred combinations (where "I" represents the compound of formula (I)) include: I+benoxacor, I+cloquintocet (including cloquintocet-mexyl);I+cyprosulfamide;I+dichlormid;I+fenchlorazole (including fenchlorazole-ethyl);I+fenclorim;I+fluxofenim;I+furilazoleI+isoxadifen (including isoxadifen-ethyl);I+mefenpyr (including mefenpyr-diethyl);I+metcamifen and I+oxabetrinil.

[0157] Particularly preferred are mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), cloquintocet (including cloquintocet-mexyl) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.

[0158] The safeners of the compounds of formula (I) may also be used as described, for example, in The Pesticide Manual, 14 th Edition (BCPC), 2006. A reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, a reference to fenchlorazole-ethyl also applies to fenchlorazole, etc., as disclosed in WO 02 / 34048.

[0159] Preferably, the mixing ratio of the compound of formula (I) to the safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0160] The compounds of formula (I) may also be used in mixtures with other agricultural chemicals, such as fungicides, nematicides or insecticides, examples of which are given in the Pesticide Manual.

[0161] The mixing ratio of the compound of formula (I) to the mixing partner is preferably 1:100 to 1000:1.

[0162] The mixtures can be advantageously used in the abovementioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula I with the mixing partner).

[0163] The present invention still further provides a method for selectively controlling weeds in a habitat containing crops and weeds, comprising applying to the habitat a weed-controlling amount of a composition according to the present invention. "Controlling" means killing, reducing or retarding growth, or preventing or reducing germination. Generally, the plants to be controlled are undesirable plants (weeds). "Habitat" means the area in which plants are growing or will grow.

[0164] The application rates of the compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the application method (pre- or post-emergence; seed dressing; application in the seed furrow; no tillage application, etc.), the crop, the weeds to be controlled, the prevailing climatic conditions and other factors governed by the application method, the application time and the target crop. The compounds of formula I according to the invention are generally applied at rates of 10 to 2000 g / ha, in particular 50 to 1000 g / ha.

[0165] Application is generally by spraying the composition, typically with a tractor-mounted sprayer for large areas, although other methods such as dusting (for dusts), drip or drench can also be used.

[0166] Useful plants on which the compositions of the present invention can be used include crops such as cereals, e.g., barley and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beets, sugar cane and turf.

[0167] Crops may also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines, fruit bushes, fruit plants and vegetables.

[0168] It should be understood that crops include those that have been made resistant to herbicides or classes of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD inhibitors) by conventional breeding methods or genetic engineering. An example of a crop that has been made resistant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield summer rapeseed (canola). Examples of crops that have been made resistant to herbicides by genetic engineering methods include, for example, glyphosate-resistant and glufosinate-resistant corn varieties available under the trade names RoundupReady and LibertyLink. In a particularly preferred embodiment, the crop is engineered to overexpress homogentisic acid solanesyltransferase, as taught, for example, in WO 2010 / 029311.

[0169] Crops should also be understood to be crops that have been rendered resistant to pests by genetic engineering methods, such as Bt maize (resistant to the corn borer), Bt cotton (resistant to the boll weevil) and even Bt potato (resistant to the Colorado potato beetle). An example of Bt maize is the Bt 176 maize hybrid from NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the Bacillus thuringiensis soil bacterium. Examples of toxins, or transgenic plants capable of synthesizing such toxins, are described in EP-A-451878, EP-A-374753, WO-A-93 / 07278, WO-A-95 / 34656, WO-A-03 / 052073 and EP-A-427529. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Either the plant crop or its seed material can be resistant to herbicides and at the same time resistant to insect feeding ("stacked transgenic events"). For example, seeds can have the ability to express the insecticidal Cry3 protein and at the same time are resistant to glyphosate.

[0170] Crops should also be understood to include crops obtained by traditional breeding methods or by genetic modification and containing so-called output traits, such as improved storage stability, higher nutritional value and improved flavor.

[0171] Other useful plants include turfgrass, for example in golf courses, lawns, parks and roadsides, or grown commercially for lawns, and ornamental plants such as flowers or shrubs.

[0172] The compositions can be used to control unwanted plants (collectively, "weeds"), including monocotyledonous species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum. These include both Sorghum and dicotyledonous species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. Weeds may also be considered crops, but may include plants that grow outside of a crop area ("escapes"), or that grow from seeds left over from a different crop that was previously planted ("volunteers"). Such volunteers or escapees may be resistant to certain other herbicides.

[0173] Various aspects and embodiments of the invention will now be illustrated in more detail by way of example, it being understood that modifications of detail can be made without departing from the scope of the invention.

[0174] Typical abbreviations used herein include the following: br=widened t Bu = tert-butyl d=double line dba = dibenzylideneacetone DCM = dichloromethane DMSO = dimethyl sulfoxide DPPA = diphenylphosphoryl azide Et2O = diethyl ether EtOAc = ethyl acetate h=time m=multiplet Me = methyl MeOH = methanol Ph = phenyl i Pr=isopropyl rt=room temperature s=single line t=triple line THF = tetrahydrofuran EXAMPLES

[0175] Example 1 Preparation of 4-[3-chloro-6-fluoro-2-[2-(4-phenylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.027) [ka] 1.1 3-Allyl-2-bromo-1-chloro-4-fluoro-benzene A solution of lithium diisopropylamide (2M in tetrahydrofuran, 3.6 ml, 7.2 mmol) was cooled to −78° C. under nitrogen. A solution of 2-bromo-1-chloro-4-fluoro-benzene (1.0 g, 4.8 mmol) in tetrahydrofuran was added dropwise at −78° C. The mixture was stirred at the same temperature for 45 min and then treated with allyl bromide (0.3 ml, 5.7 mmol). The reaction was continued at −78° C. for 2 h and then warmed to room temperature. The reaction was quenched with saturated NH4Cl(aq) and extracted with ethyl acetate. The organics were separated, retained, and then washed with brine. The organics were dried over sodium sulfate and concentrated under reduced pressure to give 3-allyl-2-bromo-1-chloro-4-fluoro-benzene (1.2 g, 100%) as an oil. [ka] 1 H NMR (400MHz, CDCl3) δ H :7.34-7.30(m,1H),7.01-6.96(m,1H),5.94-5.83(m,1H),5.10-5.00(m,2H),3.64-3.58(m,2H).

[0176] 1.2 2-(2-Bromo-3-chloro-6-fluoro-phenyl)acetic acid A solution of 3-allyl-2-bromo-1-chloro-4-fluoro-benzene (15.0 g, 60.1 mmol) in dichloromethane (200 mL) in a two-neck flask was cooled to -78°C. One side tube was connected to a trap containing an aqueous solution of KI. Ozone was bubbled through the solution until the starting material was completely consumed (5 h). Air was bubbled through the solution for 10 min to remove excess ozone. Dimethyl sulfide (44 ml, 601 mmol) was added and the mixture was allowed to warm to room temperature. The reaction was continued at room temperature for 16 h.

[0177] The mixture was washed with brine (2×100 mL) and the organic layer was retained. The organics were dried over Na2SO4, filtered and concentrated under reduced pressure to give crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g), which was used for the next step without further purification.

[0178] Crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g, 60.8 mmol) was dissolved in a mixture of tert-butanol (92 mL) and water (46 mL) and then cooled to 0° C. 2-Methylbut-2-ene (64.5 mL, 608 mmol), sodium dihydrogen phosphate (34.6 g, 243 mmol) and sodium chlorite (16.5 g, 163 mmol) were added. The mixture was stirred for 2 h and then diluted with brine (150 mL) and 2 M hydrochloric acid (150 mL). The mixture was extracted with ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous solution of sodium metabisulfite (100 mL) then dried over Na2SO4, filtered and concentrated under reduced pressure to give a pale yellow solid. The crude solid was dissolved in a mixture of water (100 mL) and 2.0 M NaOH (30 mL). The aqueous solution was washed with ethyl acetate (100 mL) and the organics were discarded. The aqueous layer was acidified by adding concentrated hydrochloric acid (20 mL), resulting in the formation of a white suspension. The mixture was extracted with ethyl acetate (3×200 mL). The combined organics were washed with brine, dried over Na2SO4, filtered and evaporated to give 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (8.0 g, 49%) as a white solid. [ka] 1 H NMR (400MHz, DMSO-d6) δ H :12.79(br.s,1H),7.67-7.59(m,1H),7.39-7.31(m,1H),3.82(s,2H).

[0179] 1.3 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (2.0 g, 7.5 mmol) in dichloromethane (20 ml) at 0° C. was added N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride [EDC·HCl] (1.4 g, 9.0 mmol), followed by dropwise addition of methylhydrazine (0.4 ml, 7.5 mmol). The temperature of the reaction mixture was maintained at 0° C. for 3 h. The reaction was then quenched with water and extracted into dichloromethane. The organics were separated, washed with brine, and dried over Na2SO4. Concentration under reduced pressure afforded crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 81%), which was used in the next step without further purification. [ka] 1 H NMR (400MHz, DMSO-d6) δ H :7.59(dd,J=8.9 and 5.4,1H),7.30(t,J=8.9,1H),4.91(s,2H),4.10(br.s,2H),3.02(s,3H).

[0180] 1.4 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic acid ethyl ester To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 6.09 mmol) in ethanol (5 ml) was added dropwise ethyl pyruvate (0.7 ml, 6.7 mmol). The reaction was heated at 80° C. for 4 hours. The reaction mixture was then cooled to room temperature and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give the desired compound 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic acid ethyl ester (1.8 g, 75%) as an off-white solid. [ka] 1 H NMR (400MHz, CDCl3) δ H :7.40-7.35(m,1H),7.04-6.98(m,1H),4.32(q,J=7.1,2H),4.24(s,2H),3.41(s,3H),2.32(s,3H),1.36(t,J=7.1,3H).

[0181] 1.5 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one 2-{[2-(2-bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic acid ethyl ester (500 mg, 1.27 mmol) was dissolved in acetonitrile (2.5 ml) and treated with 1,8-diazabicyclo[5.4.0]undec-7-ene [DBU] (0.47 ml, 3.2 mmol). The mixture was heated to 125° C. using microwave irradiation for 1 h. The reaction mixture was then evaporated under reduced pressure. The residue was dissolved in water and acidified to pH 1 with 2N hydrochloric acid. The mixture was extracted with DCM and the organics were separated and washed with brine solution. The organic solution was dried over Na2SO4 and concentrated under reduced pressure to give the crude product. The crude material was purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (340 mg, 77.1%) as an off-white solid. [ka] 1 H NMR (400MHz, DMSO-d6) δ H :11.01(s,1H),7.77-7.73(m,1H),7.39(t,J=8.7,1H),3.58(s,3H),2.24(s,3H).

[0182] 1.6 [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate To a stirred solution of 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (1.4 g, 4.02 mmol) in dichloromethane (32 ml) was added triethylamine (1.1 ml, 8.06 mmol), 4-(dimethylamino)pyridine [DMAP] (49 mg, 0.40 mmol) and isobutyryl chloride (0.6 ml, 4.83 mmol) at room temperature.

[0183] Once deemed complete, the reaction was diluted with dichloromethane and water. The organic layer was separated, dried over Na2SO4, and concentrated under reduced pressure to give the crude product. The crude material was purified by column chromatography on silica gel (eluent, ethyl acetate / hexanes gradient) to give [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.47 g, 87%). [ka] 1 H NMR (400MHz, CDCl3) δ H :7.51-7.47(m,1H),7.10-7.05(m,1H),3.82(s,3H),2.60-2.55(m,1H),2.25(s,3H),1.02-0.98(m,6H).

[0184] 1.7 4-[3-chloro-6-fluoro-2-[(E)-2-(4-phenylphenyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-2.027) [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (0.54 g, 1.3 mmol), K2CO3 (0.55 g, 3.9 mmol), trans-2-(4-phenylphenyl)vinylboronic acid (0.44 g, 2.00 mmol), PdCl2(dppf).DCM (53 mg, 0.065 mmol), 1,4-dioxane (13 ml) and HO (3.3 mL) were combined in a 20 mL microwave vial and then heated at 140 °C under microwave irradiation for 30 min.

[0185] The reaction mixture was concentrated in vacuo to remove 1,4-dioxane and then partitioned between 2N HCl (aq) and DCM. The organic layer was separated and the aqueous layer was extracted with a further portion of DCM (×2). The combined organics were concentrated in vacuo to give a crude residue which was purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give 4-[3-chloro-6-fluoro-2-[(E)-2-(4-phenylphenyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (343 mg, 53%, A-2.027)) as a yellow foam. [ka] 1 H NMR (400 MHz, chloroform) δ = 7.59-7.33 (m, 10H), 7.07 (t, J = 8.6 Hz, 1H), 7.01 (d, J = 16.4 Hz, 1H), 6.70 (d, J = 16.5 Hz, 1H), 5.63 (s, 1H), 3.73 (s, 3H), 2.28 (s, 3H)

[0186] 1.8 4-(3-chloro-6-fluoro-2-phenethyl-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.027) To a 10 mL round bottom flask was added 5% Pd / C (73 mg, 0.034 mmol) followed by a solution of 4-[3-chloro-6-fluoro-2-[(E)-2-(4-phenylphenyl)vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (308 mg, 0.69 mmol) in 10:1 (v / v) DCM / MeOH (4 mL). B2(OH)4 (325 mg, 3.45 mmol) was then added and the reaction mixture was stirred at room temperature overnight.

[0187] The reaction mixture was then filtered through Celite® eluting with 10:1 (v / v) DCM / MeOH. The filtrate was dry loaded onto silica and purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give 4-[3-chloro-6-fluoro-2-[2-(4-phenylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (299 mg, 97% yield, A-1.027) as a yellow oil that solidified on standing. [ka] 1 H NMR (400MHz, chloroform) δ = 7.57-7.52 (m, 2H), 7.50-7.40 (m, 5H), 7.37-7.30 (m, 1H), 7.07 (d, J = 8.2Hz, 2H), 7.02 (t, J = 8.6Hz, 1H), 5.47 (s, 1H), 3.75 (s, 3H), 2.88-2.80 (m, 3H), 2.27 (s, 3H)

[0188] Example 2 Preparation of 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (A-1.036) [ka] 2.1 [5-[3-chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (4.036) [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (1.10 g, 2.63 mmol) [prepared as described in Example 1] and chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (68 mg, 0.13 mmol) were combined in degassed toluene (12 mL). 4-vinylbenzonitrile (408 mg, 3.16 mmol) and Hunig's base (0.92 mL, 5.27 mmol) were then added and the reaction mixture was heated to 95° C. for 2.5 hours.

[0189] The reaction mixture was cooled to room temperature, then diluted with dichloromethane, filtered through celite, and washed with more dichloromethane. The filtrate was concentrated in vacuo and then purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give [5-[3-chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]-2-methylpropanoate (781 mg, 64% yield, A-4.036) as a white solid. [ka] 1 H NMR (400MHz, chloroform) δ=7.62-7.55(m,2H),7.45(dd,J=5.0,8.5Hz,1H),7.45-7.40(m,1H),7.13(d,J=16.5Hz,1H),7.05(t,J=8.5 Hz,1H),6.68(d,J=16.5Hz,1H),3.69(s,3H),2.65(spt,J=7.0Hz,1H),2.23(s,3H),1.11(d,J=7.0Hz,3H),1.07(d,J=7.0Hz,3H).

[0190] 2.2 [5-[3-chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.036) [5-[3-chloro-2-[(E)-2-(4-cyanophenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (900 mg, 1.93 mmol) was subjected to catalytic hydrogenation in EtOAc (20 mL) over 5% Pd / C (50% wet) catalyst (0.82 g) at 4 bar H2.

[0191] After 1.5 h, LC / MS indicated complete reaction. The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate. The filtrate was concentrated in vacuo to give a crude residue.

[0192] The residue was adsorbed onto silica and purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give [5-[3-chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (800 mg, 81% yield, A-3.036) as a white solid. [ka] 1 H NMR (400MHz, chloroform) δ=7.56-7.51(m,2H),7.42(dd,J=5.2,8.9Hz,1H),7.26-7.21(m,2H),7.00(t,J=8.9Hz,1H),3.84(s,3H),3.02-2 .92(m,1H),2.91-2.80(m,2H),2.75-2.65(m,1H),2.54(spt,J=7.0Hz,1H),2.25(s,3H),0.98(d,J=7.0Hz,3H),0.95(d,J=7.0Hz,3H).

[0193] 2.3 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (A-1.036) [[5-[3-chloro-2-[2-(4-cyanophenyl)ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (400 mg, 0.855 mmol) was dissolved in ethanol (6 mL). The mixture was treated with a solution of lithium hydroxide (108 mg, 2.56 mmol) in water (2 mL). The reaction was stirred at room temperature for 2 hours.

[0194] The reaction mixture was concentrated in vacuo to remove ethanol. The remaining aqueous solution was diluted with water (15 mL) and then acidified to about pH 3 with 2M HCl and extracted with DCM (3×10 mL). The combined organics were dried over MgSO4, filtered and concentrated in vacuo to give the crude product.

[0195] The crude product was purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]benzonitrile (83 mg, 91% yield, A-1.036)) as a white solid. [ka] 1 H NMR(400MHz,CDCl3)δ ppm 7.46-7.51(m,2H)7.26-7.31(m,1H)7.08(d,J=8.19Hz,2H)6.86(t,J=8.50Hz,1H)3.63(s,3H)2.61-2.77(m,4H)2.24(s,3H).

[0196] Example 4 Preparation of 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (A-1.028) [ka] 4.1 [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (5.00 g, 11.97 mmol, 1.0 equiv.), 6-methyl-2-vinyl-1,3,6,2-dioxazaborocane-4,8-dione (2.63 g, 14.36 mmol, 1.2 equiv.) and chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (307 mg, 0.60 mmol, 0.05 equiv.) were charged into a 250 ml round bottom flask equipped with a condenser, stir bar and nitrogen bubbler. Under a stream of nitrogen, THF (100 mL) was added followed by N,N-diisopropylethylamine (4.2 mL, 23.94 mmol, 2.0 equiv) and the mixture was heated to reflux for 3 h.

[0197] The reaction mixture was cooled to room temperature then diluted in DCM and filtered through Celite®, washing with a further portion of DCM The eluent was then concentrated to dryness.

[0198] The crude product was purified by flash column chromatography to give [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (5.91 g, 11.4 mmol, 95% yield) as an off-white solid. [ka] 1 H NMR(400MHz,DMSO-d6)δ=7.63(dd,J=5.1,8.9Hz,1H),7.31(t,J=8.9Hz,1H),6.65(d,J=18.3Hz,1H),5.68(d,J=18.3Hz,1H),4.24(dd,J =11.9,17.2Hz,2H),3.95-3.83(m,2H),3.70(s,3H),2.66(spt,J=7.0Hz,1H),2.16(s,3H),0.90(d,J=7.0Hz,3H),0.89(d,J=7.0Hz,3H)

[0199] 4.2 [5-[3-chloro-2-[2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-3.028) [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (500 mg, 0.96 mmol), K3PO4 (886 mg, 3.85 mmol) and 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (39 mg, 0.05 mmol) were added to a 20 mL microwave vial. THF (10 mL), 4-bromo-N-ethyl-2-fluoro-N-methyl-benzamide (500 mg, 1.92 mmol) and water (0.35 mL) were added and the reaction mixture was then heated to 100° C. under microwave irradiation for 2 h.

[0200] The reaction mixture was concentrated in vacuo to remove THF and then diluted with water (20 mL) and DCM (20 mL). The organic layer was separated and the aqueous layer was extracted with DCM (3×5 mL). The combined organics were dried and concentrated in vacuo to give a crude residue which was purified by column chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give [5-[3-chloro-2-[(E)-2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (397 mg, 76% yield, A-4.028) as an off-white solid.

[0201] [5-[3-chloro-2-[(E)-2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (300 mg, 0.55 mmol) was subjected to catalytic hydrogenation in EtOAc (6 mL) over 5% Pd / C (50% wet) catalyst (0.12 g) at 3 bar H2.

[0202] After 5.5 h, LC / MS indicated complete reaction. The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate / methanol. The filtrate was concentrated in vacuo to give a crude residue.

[0203] The residue was adsorbed onto silica and purified by column chromatography on silica gel (eluent, ethyl acetate / hexane gradient) to give [5-[3-chloro-2-[2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (285 mg, 95% yield, A-3.028) as a colorless gum. [ka] [NMR of a mixture of rotamers] 1H NMR (400MHz, chloroform) δ=7.42(dd,J=5.1,8.9Hz,1H),[7.25(t,J=7.2Hz,0.5H),7.21(t,J=7.5Hz,0.5H)],6.99(t,J=8.9Hz,1H),6.96(dd,J=1.2,7.5Hz ,1H),[6.89(dd,J=1.2,6.9Hz,1H),6.86(dd,J=1.2,6.9Hz,1H)],3.85(s,3 H),[3.59(q,J=7.4Hz,1H),3.24(q,J=7.4Hz,1H)],[3.08(s,1.5H),2.90(br s,1.5H)],2.88-2.78(m,3H),2.75-2.64(m,1H),2.55(spt,J=7.0Hz,1H),2.26(s,3H),[1.2 3(t,J=7.2Hz,1.5H),1.10(t,J=7.2Hz,1.5H)],0.98(d,J=7.0Hz,3H),0.96(d,J=7.1Hz,3H)

[0204] 4.3 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (A-1.028) [5-[3-chloro-2-[2-[4-[ethyl(methyl)carbamoyl]-3-fluoro-phenyl]ethyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (300 mg, 0.55 mmol) was dissolved in ethanol (3 mL). The mixture was treated with a solution of lithium hydroxide (69 mg, 1.65 mmol) in water (3 mL). The reaction was stirred at room temperature for 2 hours.

[0205] The reaction mixture was concentrated in vacuo to remove ethanol. The remaining aqueous solution was diluted with water (15 mL) and then acidified to about pH 3 with 2M HCl and extracted with DCM (3×10 mL). The combined organics were dried and concentrated in vacuo to give the crude product.

[0206] The crude product was purified by column chromatography on silica gel (eluent, gradient of DCM / methanol) to give 4-[2-[6-chloro-3-fluoro-2-(5-hydroxy-2,6-dimethyl-3-oxo-pyridazin-4-yl)phenyl]ethyl]-N-ethyl-2-fluoro-N-methyl-benzamide (224 mg, 86% yield, A-1.028) as a white solid. [ka] [NMR of a mixture of rotamers] 1 H NMR(400MHz,DMSO-d6)δ=10.86(br s,1H),7.55-7.49(m,1H),7.25-7.19(m,2H),6.95-6.89(m,2H),3.61(s,3H),3.46(q,J=7.1Hz,1H),3.12(q,J=7.1Hz, 1H),2.95(s,1.5H),2.78(s,1.5H),2.78-2.63(m,4H),2.26(s,3H),1.11(t,J=7.1Hz,1.5H),1.00(t,J=7.1Hz,1.5H).

[0207] Example 5 Preparation of [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-4.038) [ka] 5.1 [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (4.177 g, 10.00 mmol, 1.0 eq.) and tributyl(vinyl)stannane (4.384 mL, 15.00 mmol, 1.50 eq.) were dissolved in toluene (60.00 mL), and then 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (408 mg, 0.50 mmol, 0.05 eq.) was added. The reaction mixture was heated to reflux overnight.

[0208] The reaction mixture was cooled to room temperature and then concentrated in vacuo. The crude product was then purified by flash column chromatography to give [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate as an off-white solid (3.02 g, 83% yield). [ka] 1 H NMR(400MHz,CDCl3)δ=7.40(dd,J=5.1,8.7Hz,1H),6.99(t,J=8.7Hz,1H),6.65(dd,J=11.6,17.6Hz,1H),5.37 -5.30(m,2H),3.79(s,3H),2.59(spt,J=7.0Hz,1H),2.23(s,3H),1.04(d,J=7.0Hz,4H),1.03(d,J=7.0Hz,1H)

[0209] 5.2 [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (A-4.038) A stirred mixture of [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (300 mg, 1.0 equiv.), chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (21 mg, 0.05 equiv.), 1-bromo-4-cyclopropylbenzene (243 mg, 1.5 equiv.) and N,N-diisopropylethylamine (0.29 mL, 2.0 equiv.) in toluene (5 mL) was heated to reflux under nitrogen for 3 h.

[0210] The reaction mixture was cooled to room temperature then diluted with DCM and filtered through a pad of Celite eluting with a further portion of DCM The filtrate was concentrated in vacuo to give the crude product.

[0211] The crude product was purified by flash column chromatography to give [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (285 mg, 72% yield) as a pale yellow gum. [ka] 1 H NMR(400MHz,CDCl3)δ=7.41(dd,J=5.1,8.9Hz,1H),7.26-7.22(m,2H),7.02-6.98(m ,2H),6.99(t,J=8.9Hz,1H),6.93(d,J=16.5Hz,1H),6.59(d,J=16.5Hz,1H),3.71(s, 3H),2.62(spt,J=7.0Hz,1H),2.19(s,3H),1.87(tt,J=5.0,8.4Hz,1H),1.07(d,J=7. 0Hz,3H),1.06(d,J=7.0Hz,1H),0.99-0.93(m,J=2.0,8.4Hz,2H),0.73-0.64(m,2H).

[0212] Example 6 Preparation of 4-[3-chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.039) [ka] 6.1 [5-[3-chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate An oven-dried round-bottom flask was then charged with Ir(COD)Cl2 (299 mg, 0.45 mmol) and 4-diphenylphosphanylbutyl(diphenyl)phosphane (0380 mg, 0.89 mmol). The flask was evacuated and backfilled with nitrogen (x3), then THF (75 mL) was added and the reaction was stirred at room temperature for 30 min. A THF solution of [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [prepared as described in Example 4] (6.7 g, 17.8 mmol) was added dropwise and the mixture was stirred for 10 min, followed by the dropwise addition of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.02 mL, 20.8 mmol). The reaction was stirred at 60° C. overnight.

[0213] After 24 hours, the reaction was cooled to room temperature and then concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give [5-[3-chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (4.50 g, 51% yield) as a yellow solid. [ka] 1H NMR (500MHz, chloroform) δ=7.35(dd,J=5.2,8.9Hz,1H),6.90(t,J=8.6Hz,1H),3.81(s,3H),2.59(t,J=8.5Hz,2H),2.53( spt,J=7.0Hz,1H),2.24(s,3H),1.32-1.16(m,12H),1.08-1.00(m,2H),0.98(d,J=7.0Hz,3H),0.94(d,J=7.0Hz,3H).

[0214] 6.2 4-[3-chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.039) [5-[3-chloro-6-fluoro-2-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (100 mg, 0.20 mmol), 1-bromo-4-methylsulfanyl-benzene (62 mg, 0.30 mmol), chloro(2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (24 mg, 0.03 mmol), KCO (84 mg, 0.61 mmol), 1,4-dioxane (2 mL) and water (0.2 mL) were combined in a 5 mL microwave vial. The reaction mixture was then heated under microwave irradiation at 140° C. for 90 min.

[0215] The reaction mixture was cooled to room temperature, then diluted with water (10 mL), acidified with 2M HCl to pH 3 and extracted with DCM (4x). The combined organics were concentrated in vacuo and the crude product was purified by mass-directed reverse phase HPLC to give 4-[3-chloro-6-fluoro-2-[2-(4-methylsulfanylphenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one as a white solid (22 mg, 22% yield, A-1.039). [ka] 1 H NMR (400 MHz, chloroform) δ = 7.46-7.39 (m, 3H), 7.12 (d, J = 8.0 Hz, 2H), 6.98 (t, J = 8.6 Hz, 1H), 6.90 (d, J = 8.0 Hz, 2H), 3.73 (s, 3H), 2.84-2.64 (m, 4H), 2.45 (s, 3H), 2.29 (s, 3H).

[0216] Example 7 Preparation of 4-[3-chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.388) [ka] 7.1 4-[3-chloro-6-fluoro-2-[(E)-2-[4-(methylsulfanylmethyl)phenyl]vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (500 mg, 0.96 mmol), 1-bromo-4-(methylsulfanylmethyl)benzene (324 mg, 1.44 mmol), 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (41 mg, 0.05 mmol) and potassium carbonate (417 mg, 2.89 mmol) were added to a 10-20 ml microwave vial under nitrogen atmosphere. Degassed acetonitrile (11.5 mL) and water (2.9 mL) were added and the mixture was heated to 150° C. under microwave irradiation for 20 min.

[0217] The reaction mixture was concentrated to dryness. The residue was treated with water (20 ml) and the aqueous phase was acidified to pH 3 by addition of 2M HCl resulting in the formation of a precipitate. DCM (20 ml) was added to dissolve the precipitate. Brine (20 ml) was added and the phases were separated. The aqueous phase was extracted with two further portions of DCM and then the combined organic extracts were dried and concentrated directly onto silica. The crude material was purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give 4-[3-chloro-6-fluoro-2-[(E)-2-[4-(methylsulfanylmethyl)phenyl]vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (341 mg, 82% yield) as an off-white solid. [ka] 1 H NMR(500MHz,DMSO-d6)δ=10.78(br s,1H),7.60(dd,J=5.2,8.7Hz,1H),7.30-7.24(m,5H),6.93(d,J=16.5Hz,1H ),6.56(d,J=16.5Hz,1H),3.67(s,2H),3.54(s,3H),2.19(s,3H),1.94(s,3H)

[0218] 7.2 4-[3-chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.388) To a solution of 4-[3-chloro-6-fluoro-2-[(E)-2-[4-(methylsulfanylmethyl)phenyl]vinyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (335 mg, 0.78 mmol) in tetrahydrofuran (12 ml) under nitrogen atmosphere was added N,N-diisopropylethylamine (1.08 ml, 6.20 mmol). The stirred reaction mixture was heated to 70° C. and 2,4,6-triisopropylbenzenesulfonylhydrazide (2.06 g, 6.21 mmol) was added in portions over 6 hours, and the mixture was then heated to reflux for 16 hours. Additional N,N-diisopropylethylamine (0.68 ml, 3.89 mmol) was added to the reaction mixture, followed by 2,4,6-triisopropylbenzenesulfonylhydrazide (1.29 g, 3.89 mmol) and the mixture was heated to reflux for a further 6 hours.

[0219] The reaction mixture was cooled to room temperature and then concentrated directly onto silica. The crude material was partially purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate. The resulting material was further purified by mass-directed reverse phase HPLC to give 4-[3-chloro-6-fluoro-2-[2-[4-(methylsulfanylmethyl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one as a white solid (208 mg, 62% yield, A-1.388). [ka] 1 H NMR(400MHz,d6-DMSO),δ=10.83(s,1H),7.56-7.53(m,1H),7.23-7.16(m,3H),6.96 -6.94(d,2H),3.62(s,2H),3.60(s,3H),2.68-2.54(m,4H),2.26(s,3H),1.92(s,3H)

[0220] Example 8 4-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.385) [ka] 8.1 [4-(1,2,4-triazol-1-yl)phenyl]trifluoromethanesulfonate 4-(1,2,4-Triazol-1-yl)phenol (1.22 g, 7.57 mmol) was dissolved in dichloromethane (10 ml) under nitrogen and cooled to approximately 0° C. A solution of pyridine (1.22 ml, 15.1 mmol) in dichloromethane (5 ml) was added dropwise over approximately 2 minutes. The mixture was stirred for 5 minutes and then a solution of trifluoromethanesulfonic anhydride (1.53 ml, 9.08 mmol) in dichloromethane (5 ml) was added dropwise over approximately 2 minutes. The cooling was removed and the reaction mixture was allowed to warm to room temperature and then stirred at room temperature for 16 hours.

[0221] The reaction was quenched by the addition of 2M aqueous HCl (20 ml) and then the organic phase was separated. The aqueous phase was further extracted with dichloromethane (2 x 20 ml). The combined organics were washed with water (20 ml), dried and then concentrated under reduced pressure to give a cream solid. The crude material was purified by automated flash chromatography on silica eluting with a gradient of cyclohexane / ethyl acetate to give [4-(1,2,4-triazol-1-yl)phenyl]trifluoromethanesulfonate as a white solid (2.02 g, 91% yield). [ka] 1 H NMR (400 MHz, chloroform) δ = 8.59 (s, 1H), 8.14 (s, 1H), 7.86-7.78 (m, 2H), 7.50-7.41 (m, 2H).

[0222] 8.2 [5-[3-chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (500 mg, 0.96 mmol), 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (39 mg, 0.048 mmol), [4-(1,2,4-triazol-1-yl)phenyl]trifluoromethanesulfonate (367 mg, 1.25 mmol) and potassium phosphate (834 mg, 3.85 mmol) were added to a 10-20 ml microwave vial.

[0223] Tetrahydrofuran (10 ml) and water (0.5 ml) were added and the reaction mixture was then degassed by stirring under vacuum and then backfilled with nitrogen (x3). The reaction mixture was heated under microwave irradiation in a microwave at 120° C. for 60 minutes.

[0224] The reaction mixture was filtered through a plug of Celite® and washed with EtOAc and EtOH. The filtrate was concentrated under reduced pressure to give a brown gum (840 mg). The crude material was purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate to give a pale yellow gum (389 mg). The purified material was dissolved in acetonitrile (10 ml) and treated with SiliCycle SiliaMetS® thiol (SH) metal scavenger resin (365 mg) at room temperature. The suspension was stirred at room temperature for 3 hours, then filtered to remove the resin and washed with more acetonitrile. The filtrate was concentrated in vacuo to give [5-[3-chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate as a colorless gum (361 mg, 73% yield). [ka] 1 H NMR (400MHz, chloroform) δ ppm 8.55(s,1H), 8.11(s,1H), 7.60-7.66(m,2H), 7.42-7.53(m,3H), 7.01-7.10(m,2H), 6.69(d,J=16.5Hz,1H), 3.70(s,3H), 2.66(spt,J=7.0Hz,1H), 2.23(s,3H), 1.11(d,J=7.0Hz,1H), 1.08(d,J=7.1Hz,1H)

[0225] 8.3 [5-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (A-3.385) [5-[3-Chloro-6-fluoro-2-[(E)-2-[4-(1,2,4-triazol-1-yl)phenyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (365 mg, 0.72 mmol) was subjected to catalytic hydrogenation in EtOAc (10 mL) over 5% Pd / C (50% wet) catalyst (0.15 g) at 3 bar H for 24 h.

[0226] The reaction mixture was filtered through a pad of Celite® and washed with ethyl acetate. The filtrate was concentrated in vacuo to give a crude residue (350 mg) that was adsorbed onto silica and purified by automated flash chromatography on silica gel eluting with a gradient of cyclohexane / ethyl acetate. [5-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (A-3.385) was obtained as a colorless gum (321 mg, 88% yield). [ka] 1 H NMR (400MHz, chloroform) δ=8.51(s,1H),8.09(s,1H),7.55(d,J=8.2Hz,2H),7.43(dd,J=5.2,8.7Hz,1H),7.27(d,J=8.2Hz,2H),7.00(t,J=8.7H) z,1H),3.84(s,3H),2.97-2.80(m,3H),2.79-2.67(m,1H),2.55(spt,J=7.0Hz,1H),2.25(s,3H),0.98(d,J=7.0Hz,3H),0.96(d,J=7.0Hz,1H)

[0227] 8.4 4-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.385) [5-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (320 mg, 0.63 mmol) was stirred in ethanol (5 ml) at room temperature.

[0228] A solution of lithium hydroxide monohydrate (81 mg, 1.88 mmol) in water (2 ml) was added dropwise and the reaction stirred at room temperature for 1 hour.

[0229] The ethanol solvent was removed under reduced pressure and the residue was diluted with water (20 ml). The aqueous phase was acidified to about pH 3-4 by addition of 2M HCl (aq) and then extracted with EtOAc (3×10 ml). The combined organic extracts were concentrated under reduced pressure to give a white solid (292 mg). The crude residue was purified by automated flash chromatography on silica eluting with gradients of cyclohexane / ethyl acetate and ethyl acetate / ethanol to give 4-[3-chloro-6-fluoro-2-[2-[4-(1,2,4-triazol-1-yl)phenyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (A-1.365) as a white solid (260 mg, 94% yield). [ka] 1 H NMR (400MHz, methanol), δ ppm 9.03(s,1H),8.14(s,1H),7.65-7.70(m,2H),7.51(dd,J=5.2,8.7Hz,1H),7. 20(m,2H),7.11(t,J=8.7Hz,1H),3.72(s,3H),2.72-2.89(m,4H),2.32(s,3H)

[0230] Example 9 4-[3-Cyclopropyl-6-fluoro-2-[2-(2-fluoro-4-pyridyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (C-1.013) [5-[3-chloro-6-fluoro-2-[2-(2-fluoro-4-pyridyl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (250 mg, 0.54 mmol), tripotassium phosphate monohydrate (374 mg, 1.62 mmol) and RuPhos Pd G2 (42 mg, 0.05 mmol) were charged into a 2-5 ml microwave vial equipped with a stir bar. The reaction vessel was evacuated and backfilled with nitrogen (x3). 1,4-Dioxane (4 ml) was added followed by cyclopropylboronic acid (139 mg, 1.62 mmol) and water (1 ml) (both solvents were degassed). The mixture was then heated to 120 °C under microwave irradiation for 1 h.

[0231] The reaction was cooled to room temperature, then additional cyclopropylboronic acid (139 mg, 1.62 mmol) and RuPhos Pd G2 (42 mg, 0.05 mmol) were added and the reaction was heated to 120° C. for an additional 2.5 h: The reaction mixture was concentrated in vacuo to remove dioxane. The residue was diluted with water (20 ml) and DCM (20 mL) and the layers were separated. The aqueous phase was extracted with a further portion of DCM (3×5 ml) and the combined organic extracts were then dried and concentrated to give a dark solid (331 mg).

[0232] The crude residue was purified by mass-directed reverse phase HPLC to give 4-[3-cyclopropyl-6-fluoro-2-[2-(2-fluoro-4-pyridyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (C-1.013) as a white solid. [ka] 1H NMR (400MHz, methanol) δ=8.01(d,J=5.1Hz,1H),7.13(dd,J=5.6,8.3Hz,1H),7.02-6.93(m,2H),6.72(br s,1H),3.72(s,3H),3.02-2.75(m,4H),2.32(s,3H),1.97-1.87(m,1H),1.02-0.89(m,2H),0.74-0.61(m,2H)

[0233] Compounds A-1.023, A-1.024, A-1.025, A-1.026, A-1.027, A-1.028, A-1.029, A-1.030, A-1.031, A-1.032, A-1.033, A-1.034, A-1.035, A-1.03 6, A-1.037, A-1.038, A-1.039, A-1.040, A-1.041, A-1.042, A-1.043, A-1.044, A-2.027, A-2.030, A-2.037, A-3.028, A-3.029, A-3.030 , A-3.035, A-3.036, A-3.038, A-4.029, A-4.030, A-4.035, A-4.036, A-1.373, A-1.374, A-1.375, A-1.376, A-1.377, A-1.378, A-1.379, A-1.380, A-1.381, A-1.382, A-1.383, A-1.384, A-1.386, A-1.387, A-1.389, A-1.390, A-1.391 and A-1.392 were prepared using the general method described above. Table 4 below shows the structures and NMR characterization data of these compounds.

[0234] [Table 4-1] [Table 4-2] [Table 4-3] [Table 4-4] [Table 4-5] [Table 4-6] [Table 4-7] [Table 4-8] [Table 4-9] [Table 4-10] [Table 4-11] [Table 4-12] [Table 4-13] [Table 4-14] [Table 4-15] [Table 4-16] [Table 4-17]

[0235] B1 Post-emergence efficacy – Test 1 Seeds of different test species are sown in standard soil in pots:- Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). After 8 days (after emergence) of cultivation under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from a formulation of technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). The compounds are applied at 1000 g / ha. The test plants are then grown in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the test is evaluated for the percentage of damage caused to the plants. Biological activity is assessed on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Blank values ​​in the tables indicate that the compound was not tested on that species.

[0236] [Table 5]

[0237] B2 Post-emergence efficacy – Study 2 Seeds of the different test species are sown in standard soil in pots:- Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). After 8 days of cultivation (post-emergence) in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from a formulation of technical active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). The compounds are applied at 250 g / ha. The test plants are then grown in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the test is evaluated for the percentage of damage caused to the plants. Biological activity is rated on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). The blank values ​​in the table indicate that the compound was not tested on the corresponding species.

[0238] [Table 6]

[0239] B3 Post-emergence efficacy – Study 3 Seeds of the different test species are sown in standard soil in pots:- Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Zea mays (ZEAMX), Abutilon theophrasti (ABUTH). After 8 days of cultivation (post-emergence) in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants are sprayed with a spray solution derived from a formulation of technical active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Compounds are applied at 250 g / ha. Test plants are then grown in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests are evaluated for the percentage of damage caused to the plants. Biological activity is assessed on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Blank values ​​in the tables indicate that the compound was not tested on that species.

[0240] [Table 7]

[0241] B4 Pre-emergence efficacy – Study 1 Seeds of the different test species were sown in standard soil in pots: Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). After 1 day of cultivation (before emergence) in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with a spray solution derived from a formulation of technical active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Compounds are applied at 1000 g / ha. Test plants are then grown under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests are evaluated for the percentage of damage caused to the plants. Biological activity is assessed on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Blank values ​​in the tables indicate that no compound was tested on that species.

[0242] [Table 8]

[0243] B5 Pre-emergence efficacy – Study 2 Seeds of the different test species were sown in standard soil in pots: Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). After 1 day of cultivation (before emergence) in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with a spray solution derived from a formulation of technical active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Compounds are applied at 250 g / ha. Test plants are then grown under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests are evaluated for the percentage of damage caused to the plants. Biological activity is assessed on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Blank values ​​in the tables indicate that no compound was tested on that species.

[0244] [Table 9]

[0245] B6 Pre-emergence efficacy – Study 3 Seeds of the different test species were sown in standard soil in pots: Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Zea mays (ZEAMX), Abutilon theophrasti (ABUTH). After 1 day of cultivation (pre-emergence) in a greenhouse under controlled conditions (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with a spray solution derived from a formulation of technical active ingredients in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN9005-64-5). Compounds are applied at 250 g / ha. Test plants are then grown under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests are evaluated for the percentage of damage caused to the plants. Biological activity is assessed on a 5-point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Blank values ​​in the tables indicate that no compound was tested on that species.

[0246] [Table 10]

Claims

1. Compounds of formula (I) 【Chemistry 1】 or a salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, Amino, C 1 ~C 6 Alkylamino, C 1 ~C 6 Dialkylamino, -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; Each R 4a and R 5a is C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4a and R 5a can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X and Y are each independently hydrogen, C 1 ~C 3 Alkyl, cyclopropyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; D is R on at least one ring carbon atom. 8 and / or substituted on at least one ring nitrogen atom with R 9 is a substituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, substituted with At least one R 8 is C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, -NR 4a R 5a , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 and a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; At least one R 9 is C 5 ~C 6 Alkyl, C 5 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 3 Alkyl-, C 3 Alkoxy-C 1 ~C 2 Alkyl-, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl- and a ring system selected from the group consisting of a phenyl ring, a 5- to 6-membered heteroaryl ring, and a 3- to 6-membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; Alternatively, D is at least one R 8 is a phenyl ring substituted with; W is 【Chemistry 2】 where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; However, R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

2. Compounds of formula (I) 【Chemistry 3】 or a salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, -NR 4 R 5 , -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X is cyclopropyl; Y is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is selected from the group consisting of R 8 and / or substituted on the ring nitrogen atom with R 9 is substituted with; Each R 8 are independently oxygen, hydroxyl, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl-, -NR 4 R 5 , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 9 are independently 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is substituted with; W is 【Chemistry 4】 where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl, where R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

3. Compounds of formula (I) 【Chemistry 5】 or a salt or N-oxide thereof [In the formula, R 1 is C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 3 ~C 6 Alkoxy, C 1 ~C 2 Alkoxy-C 1 ~C 2 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, Cyano-C 1 ~C 4 Alkyl, C 2 ~C 4 Haloalkenyl, C 2 ~C 4 Alkynyl and C 2 ~C 4 haloalkynyl; R 2 is hydrogen, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, -S(O) m C 1 ~C 6 Alkyl, -NR 4 R 5 , -C(C 1 ~C 3 alkyl)=N-O-C 1 ~C 3 Alkyl and C 2 ~C 6 haloalkynyl; G is hydrogen or C(O)R 3 and R 3 is C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 1 ~C 6 Alkyl-S-, C 1 ~C 6 Alkoxy, -NR 4 R 5 and one or more R 6 phenyl optionally substituted with; Each R 4 and R 5 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, and C 3 ~C 6 cycloalkyl; or R 4 and R 5 can be taken together to form a morpholinyl ring; R 6 is halogen, cyano, nitro, C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy and C 1 ~C 3 haloalkoxy; X is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkyl, C 1 ~C 3 haloalkoxy, or halogen; Y is cyclopropyl; D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen, and sulfur, and when D is substituted, it is selected from the group consisting of R 8 and / or substituted on the ring nitrogen atom with R 9 is substituted with; Each R 8 are independently oxygen, hydroxyl, halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Haloalkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 6 Hydroxyalkyl-, C 1 ~C 6 Alkylcarbonyl-, C 1 ~C 6 Haloalkylcarbonyl-, C 3 ~C 6 Cycloalkylcarbonyl-, -S(O) m -C 1 ~C 6 Haloalkyl, -S(O) m -C 3 ~C 6 Cycloalkyl, -O-S(O) 2 C 1 ~C 3 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -Alkyl, -NR 4 R 5 , -C(S)NR 4 R 5 , -S(O) 2 NHC(O)C 1 ~C 3 Alkyl, -S(O) 2 N.R. 4 R 5 , -C(O)OH, -C(O)OC 1 ~C 6 Alkyl, -C(O)NHS-(O) 2 C 1 ~C 6 Alkyl, —C(O)NR 4 R 5 , -NR 4 C(O)NR 4 R 5 , C 1 ~C 6 Alkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylcarbonylamino-, C 1 ~C 6 Haloalkylcarbonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Alkylsulfonylamino-, C 1 ~C 6 Alkyl sulfonyl (C 1 ~C 6 alkyl)amino-, C 1 ~C 6 Haloalkylsulfonylamino-, C 1 ~C 6 Haloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, C 3 ~C 6 Cycloalkylsulfonylamino-, C 3 ~C 6 Cycloalkylsulfonyl (C 1 ~C 6 alkyl)amino-, hydroxyamino-, hydroxy(C 1 ~C 6 alkyl)amino, C 1 ~C 6 Alkoxyamino, C 1 ~C 6 Alkoxy (C 1 ~C 6 alkyl)amino, C 1 ~C 6 Haloalkoxyamino, C 1 ~C 6 Haloalkoxy (C 1 ~C 6 or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; m is an integer of 0, 1, or 2; Each R 9 are independently 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 -Cycloalkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl-, C 1 ~C 6 Hydroxyalkyl-, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Alkyl, -C 1 ~C 3 Alkyl-S(O) m -C 1 ~C 6 Haloalkyl, -C 1 ~C 3 Alkyl-S(O) m -C 3 ~C 6 Cycloalkyl, cyano-C 1 ~C 6 -alkyl-, or a ring system selected from the group consisting of a phenyl ring, a 5-6 membered heteroaryl ring, and a 3-6 membered heterocyclyl ring, said ring system being selected from the group consisting of 0-5 R 16 is substituted with; Each R 16 are independently halogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy or C 1 ~C 6 is haloalkoxy; or D is a substituted or unsubstituted phenyl ring, and when said phenyl ring is substituted it is selected from 1 to 5 R 8 is substituted with; W is 【Chemistry 6】 where: "a" represents the point of attachment to the phenyl-pyridazinedione / phenyl-pyridazinone moiety; "b" represents the point of attachment to ring D; R 10 , R 12 , R 14 and R 15 are each independently hydrogen, C 1 ~C 3 Alkyl, or C 1 ~C 3 Is it haloalkyl; Or R 10 and R 12 together with the carbon atom to which they are attached, C 3 ~C 6 forming a carbocyclic ring; R 11 and R 13 are each independently hydrogen, halogen, or C 1 ~C 3 Alkyl, or C 1 ~C 3 haloalkyl, where R 11 Or R 13 One of them is halogen, C 1 ~C 3 Alkyl or C 1 ~C 3 when one is haloalkyl, the other is hydrogen.

4. G is hydrogen or -C(O)R 3 and R 3 But, C 1 ~C 4 Alkyl, C 2 ~C 3 Alkenyl, C 2 ~C 3 Alkynyl, C 1 ~C 4 Alkoxy, -NR 4 R 5 and R 4 and R 5 The compound according to any one of claims 1 to 3, wherein together form a morpholinyl ring, or phenyl.

5. G is hydrogen or C(O)R 3 and R 3 The compound according to any one of claims 1 to 4, wherein is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy.

6. X is hydrogen, C 1 ~C 3 Alkyl, halogen, or C 1 6. The compound of claim 1, 3, 4, or 5, which is a haloalkyl.

7. Y is hydrogen, C 1 ~C 3 Alkyl, C 1 ~C 3 7. The compound of claim 1, 3, 4, 5, or 6, which is haloalkyl or halogen.

8. A compound according to any one of claims 1 to 7, wherein X is ortho with respect to the pyridazinone / pyridazinedione moiety.

9. The compound of any one of claims 1 to 8, wherein Y is ortho relative to the -WD moiety.

10. R 1 is methyl, ethyl, n-propyl, cyclopropyl, propargyl, or C 1 The compound of any one of claims 1 to 9, which is haloalkyl.

11. R 2 But hydrogen, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 6 Alkoxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 3 ~C 6 Cycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl and C 2 ~C 6 The compound of any one of claims 1 to 10, selected from the group consisting of haloalkynyl.

12. The compound of any one of claims 1 to 11, wherein D is a substituted or unsubstituted monocyclic heteroaryl ring.

13. The compound of any one of claims 1 to 11, wherein D is a substituted or unsubstituted phenyl ring.

14. W is W1, R 10 , R 11 , R 12 , and R 13 The compound of any one of claims 1 to 13, wherein each of is hydrogen.

15. W is W2, R 14 and R 15 The compound of any one of claims 1 to 13, wherein each of is hydrogen.

16. The compound according to any one of claims 1 to 13, wherein W is W3.

17. 17. A herbicidal composition comprising the herbicidal compound according to any one of claims 1 to 16 and an agriculturally acceptable formulation auxiliary.

18. 20. The herbicidal composition of claim 17 further comprising at least one additional pesticide.

19. 20. The herbicidal composition of claim 18, wherein the additional pest control agent is a herbicide or a herbicide safener.

20. A method for controlling undesirable plant growth, comprising the step of applying a compound of formula (I) as defined in any one of claims 1 to 16, or a herbicidal composition as defined in any one of claims 17 to 19, to said undesirable plants or to the locus thereof.

21. Use of a compound of formula (I) according to any one of claims 1 to 16 as a herbicide.

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